Cyclopropenium polymers and methods for making the same

ABSTRACT

The present invention provides, inter alia, a process for incorporating a cyclopropenium ion into a polymeric system. Processes for making cross-linked polymers, linear polymers, and dendritic polymers, as well as for incorporating a cyclopropenium ion onto a preformed polymer are also provided. Further provided are stable, polycationic compounds, various polymers that contain stable cyclopropenium cations, and substrates containing such polymers. The use of these polymers in water purification systems, antimicrobial coatings, ion-transport membranes, cell supports, drug delivery vehicles, and gene therapeutic vectors are also provided.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional application of and claims priority fromU.S. application Ser. No. 14/611,166, filed on Jan. 30, 2015, which is aContinuation in Part of International Application No. PCT/US2013/052679,which was filed on Jul. 30, 2013, and which claims priority to U.S.Provisional Application No. 61/677,837, which was filed on Jul. 31,2012, which applications are incorporated by reference in theirentireties as if recited in full herein. U.S. application Ser. No.14/611,166, filed on Jan. 30, 2015, also claims priority to U.S.Provisional Application No. 62/092,726, filed Dec. 16, 2014, the entirecontents of which are incorporated by reference.

FIELD OF INVENTION

The present invention provides, inter alia, processes for incorporatinga cyclopropenium ion into a polymeric system, for making cross-linkedpolymers, linear polymers, and dendritic polymers, as well as forincorporating a cyclopropenium ion onto a preformed polymer. Furtherprovided are substrates made from such processes.

BACKGROUND OF THE INVENTION

Modularly designed polymeric materials can be engineered to suit a broadrange of applications representing an attractive platform fortechnological advancement. Materials that possess both inherentcompositional versatility and ready accessibility via robust andscalable synthetic pathways are of particular import to the field (Huntet al. 2011, Leibfarth et al. 2010). In this regard, cationicpolyelectrolytes have emerged as a versatile class of materials thathave been exploited in a broad array of applications (Lodge 2008, Gao etal. 2012, Hallinan et al. 2013), ranging from gene delivery (De Smedt etal. 2000, Samal et al. 2012) to ion-conducting membranes (Pan et al.2011, Hickner et al. 2013, Chen et al. 2010), and water purification(Elimelech et al 2011, Gin et al. 2011). Development in the area ofcationic polyelectrolytes has thus far focused on a limited menu ofmonomeric functionalities, including ammonium, phosphonium, imidazolium,pyridinium and guanidinium ions (Jangu et al. 2014, Qiu et al. 2012,Yuan et al. 2013). These heteroatomic systems, while valuable, areapplication specific and suffer from the ability to finely tune theirphysical properties. Thus, the identification of new modular cationicpolyelectrolytes, with superior characteristics for processing,controllable self-assembly and function, represents an important goalfor this field (Sing et al. 2014, Steele et al. 2001). In developing anew family of polyelectrolytes, certain criteria must be met (Chen etal. 2010, Gin et al. 2011, Sing et al. 2014) including: (1)thermodynamic stability; (2) ease and scalability of polymerisations bycontrolled methods; (3) incorporation of accessible chemical handles toallow for diversity and intimate control of physical properties and (4)tunable Coulombic interactions. As an outgrowth of ongoing researchefforts, it was postulated that polyelectrolytes based on thecyclopropenium ion could satisfy these design criteria, while offering ahighly distinct structural architecture and electronic properties. Itwas further recognized that such cyclopropenium-based systems possessunique characteristics that distinguish them from existing cationicpolyelectrolytes, namely: enhanced dispersion of the positive charge(compared with ammonium, phosphonium and guanidinium systems) and weakerH-bond donor capacity (compared with imidazolium and pyridinium ions)(Curnow et al. 2011).

As the smallest of the Hückel aromatics (Hückel 1938), thecyclopropenium (CP) ion possesses significant stability despite itscarbocationic nature (Breslow 1957, Bandar et al. 2013b). Thisremarkable degree of stability may be further enhanced through theincorporation of amino substituents onto the CP ring (Yoshida et al(1971). Indeed, with pK_(R+) values estimated at >13,aminocyclopropenium ions are stable even in strongly alkaline aqueoussolutions (Yoshida et al. 1974, Kerber et al. 1973). Moreover, thermaldecomposition (T_(dec)) of the tris(dialkylamino)CP chloride salts hasbeen measured at >300° C. (Curnow et al. 2011), significantly exceedingthat of dialkylimidazolium chloride salts (T_(dec), 250° C.) (Huddlestonet al. 2001). These unique structural features have already inspired thedevelopment of aminocyclopropenium ions for a range of applications,including as metal ligands (Bruns et al. 2010), organocatalysts (Banderet al. 2012, Bander et al. 2013, Wilde et al. 2013) and ionic liquids(Curnow et al, 2011); however, the incorporation of these cations into apolymeric backbone has only led to polymers with unstable CP ions asintermediates (Weidner et al. 1995). Given the tunable functionality androbust, efficient and orthogonal chemistry characterizing CP ions, it isdesirable to exploit them in polymeric materials.

Indeed, the ability to incorporate stable ionic moieties on linear,branched, dendritic, and cross-linked polymeric systems has led to thedevelopment of materials that can be employed in a wide variety ofapplications, such as water purification, drug delivery, gene therapy,antimicrobial coatings, ion transporting membranes, and as cellsubstrates, among others. For example, water desalination membranes arecurrently being synthesized by cross-linking polymerization of1,3-benzenediamine and trimesoyl chloride, to yield a polyelectrolyte.Other materials, such as electrostatic layers have also been evaluated.Starpharma has developed dendritic polyelectrolytes based onpolyamidoamine (PAMAM) as HIV prevention drugs and for drug delivery.Drug delivery vectors containing guanidine have also been shown to beeffective mimics of cell-penetrating peptides.

Such polymers are desirable for many reasons, but available materialssuffer from a number of limitations, such as pH sensitivity, difficultyof synthesis, or lack of variability. For example, in water purificationmembranes, currently available materials lack tunable mechanicalproperties and can be brittle. Furthermore, the chemistry is moredifficult to manage due to the fact that the acid chlorides that arecurrently used are water sensitive, and must be processed in dryconditions.

Accordingly, there is a need for, inter alia, stable ionic moieties onlinear, branched, dendritic, and cross-linked polymeric systems that aresimple to prepare, are broadly tunable in terms of their properties, andare stable across a wide range of pH levels. The present invention isdirected to meeting these and other needs.

SUMMARY OF THE INVENTION

Here, the synthesis and evaluation of a new family of cationicpolyelectrolytes is described. As outlined in FIG. 4b , a vision for thedesign of the parent ionic monomer includes a polymerisable unit, aspectator group (which could also serve as a functional handle) and fouradditional modular groups that provide the means to tune the physicalproperties of the resulting macromolecules. These initial studies,focused on styrenic CP monomers (termed, CPR) bearing a series ofdialkylamino (NR₂) substituents. Styrene-based monomers can be subjectedto various reversible-deactivation radical polymerization strategies(Hawker et al. 2001, Matyjaszewsld et al. 2001, Chiefari et al. 1998).Reversible-addition fragmentation chain transfer (RAFT) polymerization(Chiefari et al. 1998) was used to assemble homopolymers, statisticalcopolymers and diblock copolymers of different compositions ranging from20 to 50 mol % of CP functionality. It was demonstrated thatmacromolecular assemblies of these materials can be used asion-conducting membranes, and that the physical properties of theseassemblies may be tuned through variation of the dialkylamino handles.In addition, it was demonstrated that CPR monomers undergo asurfactant-free emulsion polymerization with styrene, yielding welldefined, sub-100 nm nanoparticles with charged surfaces.

The inventors have discovered the ability to incorporate acyclopropenium cation (CPC) into polymeric architectures and modularplatforms and to exploit these materials in applications where stablepolycationic species are desired. The CPC is an esoteric functionalgroup in materials chemistry. It has the unique ability to remainpositively charged at high pH, a property that is difficult to matchwith any other functional group. Conventional materials having ionicmoieties integrated into polymeric systems traditionally have used basicunits that are protonated (such as amines), and these materials tend tolose their charge at pHs above 7. Due to the loss of charge atphysiological conditions, such conventional materials are less efficientin their respective applications, including but not limited todesalinization, drug delivery, surface coatings, antimicrobial coatings,etc. In contrast, the stable polycationic materials of the presentinvention are simple to prepare, are broadly tunable in terms of theirproperties, and are stable in pHs ranging from 0 to greater than 14.Thus, the stable polycationic materials of the present invention willprovide unparalleled performance for drug delivery, DNA binding,desalinization, and myriad other applications.

In this regard, one embodiment of the present invention is a process forincorporating a cyclopropenium ion into a polymeric system. This processcomprises contacting a functionalized cyclopropenium ion with afunctionalized compound capable of reacting with the functional group ofthe cyclopropenium ion for a period of time and under conditionssuitable for the functionalized cyclopropenium and the functionalizedcompound to react and form a polymeric system that comprises a stablecyclopropenium cation that remains positively charged at a high pH.

Another embodiment of the present invention is a process for making across-linked polymer. This process comprises contacting an alkenefunctionalized cyclopropenium ion with a polymer comprising a pendantthiol group, for a period of time and under conditions suitable for thefunctionalized cyclopropenium ion and the polymer to react and form across-linked polymer that comprises a stable cyclopropenium cation thatremains positively charged at a high pH.

Yet another embodiment of the present invention is a process for makinga cross-linked polymer. This process comprises contacting a thiolfunctionalized cyclopropenium ion with a functionalized compoundcomprising an alkene group, for a period of time and under conditionssuitable for the functionalized cyclopropenium ion and thefunctionalized compound to react and form a cross-linked polymer thatcomprises a stable cyclopropenium cation that remains positively chargedat a high pH.

A further embodiment of the present invention is a process for making alinear polymer. This process comprises contacting a functionalizedcyclopropenium ion with a polymerizing agent for a period of time andunder conditions suitable for the functionalized cyclopropenium ion toreact and to form a linear polymer that comprises a stablecyclopropenium cation that remains positively charged at a high pH.

An additional embodiment of the present invention is a process forincorporating a cyclopropenium ion onto a preformed polymer. Thisprocess comprises contacting a cyclopropenium ion functionalized toparticipate in a click reaction with a preformed polymer backbone havinga pendant group that is functionalized with a complementary groupsuitable for participating in a click reaction with the cyclopropeniumion for a period of time and under conditions suitable for thefunctionalized cyclopropenium ion and the preformed polymer to react viaa click chemistry mechanism and form a polymer that comprises a stablecyclopropenium cation that remains positively charged at a high pH.

Another embodiment of the present invention is a process for making adendritic polymer. This process comprises the steps of:

a. providing a first functionalized compound comprising a cyclopropeniumion, which has a reactive group at each position of the ring; and

b. grafting a second functionalized compound onto each reactive group ofthe first functionalized compound such that chemical bonds are formedbetween the first functionalized compound and the second functionalizedcompound at the reactive groups, the second functionalized compoundincluding reactive groups capable of forming bonds with the reactivegroups on the cyclopropenium ion, and wherein the bonds are formedthrough a click chemistry mechanism.

An additional embodiment of the present invention is a stable,polycationic compound made by any process disclosed herein.

A further embodiment of the present invention is a polymer thatcomprises a stable cyclopropenium cation that remains positively chargedat a high pH, the polymer having the structure:

whereinX₁₋₂ are independently selected from the group consisting of Cl, N, andany other atom suitable for participating in the process;R₁₋₂ are independently selected from the group consisting of no atom,amino, aryl, heteroaryl, C₁₋₁₀alkoxy, C₂₋₁₀alkenyloxy, C₂₋₁₀alkynyloxy,C₁₋₁₀alkyl, C₃₋₁₀cycloalkyl, C₂₋₁₀alkenyl, C₃₋₁₀cycloalkenyl,C₂₋₁₀alkynyl, halogen, aryloxy, heteroaryloxy, C₂₋₁₀alkoxycarbonyl,C₁₋₁₀alkylthio, C₂₋₁₀alkenylthio, C₂₋₁₀alkynylthio, C₁₋₁₀alkylsulfonyl,C₁₋₁₀alkylsulfinyl, aryl-C₁₋₁₀alkyl, heteroaryl-C₁₋₁₀alkyl,aryl-C₁₋₁₀heteroalkyl, heteroaryl-C₁₋₁₀heteroalkyl, a phosphorus group,a silicon group and a boron group, wherein R₁ and R₂ are optionallycombined to form a 5 to 8-membered carbocyclic or heterocyclic ring;further wherein the aliphatic or aromatic portions of R₁ and R₂ areoptionally substituted with from 1 to 4 substituents selected from thegroup consisting of halogen, cyano, nitro, C₁₋₄alkyl, C₂₋₆alkenyl,C₂₋₆alkynyl, aryl, C₁₋₆alkoxy, C₂₋₆alkenyloxy, C₂₋₆alkynyloxy, aryloxy,C₂₋₆alkoxycarbonyl, C₁₋₆alkylthio, C₁₋₆alkylsulfonyl, C₁₋₆alkylsulfinyl,oxo, imino, thiono, primary amino, carboxyl, C₁₋₆alkylamino,C₁₋₆dialkylamino, amido, nitrogen heterocycles, hydroxy, thiol andphosphorus;

represents a suitable linking group; andn is an integer.

Another embodiment of the present invention is a cross-linked polymer.This polymer comprises a stable cyclopropenium cation that remainspositively charged at a high pH, the cross-linked polymer having thestructure:

wherein

represents a suitable linking group; andpolymer is any polymer that can be bonded to the cyclopropenium ion.

An additional embodiment of the present invention is a dendrimer having(1) a cationic core comprising a tri-functional cyclopropenium monomerand (2) at least two ordered dendritic core branches which (a) arecovalently bonded to the cationic core, (b) extend through at least twogenerations, and (c) have at least 3 terminal groups per core branch.

A further embodiment of the present invention is a substrate. Thissubstrate comprises a stable, polycationic compound made by any processdisclosed herein.

Another embodiment of the present invention is a support coated with anysubstrate disclosed herein for use in a water purification system.

Additional embodiments of the present invention include an antimicrobialcoating, an ion-transport membrane, and a cell support, each of whichcomprises a substrate as disclosed herein.

Yet another embodiment of the present invention is a drug deliveryvehicle comprising a stable cationic dendritic polymer made according toany method disclosed herein.

A further embodiment of the present invention is a gene therapeuticvector comprising a stable cationic dendritic polymer made according toany method disclosed herein.

Another embodiment of the present invention is a process forincorporating a cyclopropenium ion into a polymeric system. This processcomprises contacting a functionalized cyclopropene with a functionalizedcompound capable of reacting with the functionalized cyclopropene for aperiod of time and under conditions suitable for the functionalizedcyclopropene and the functionalized compound to react and form apolymeric system that comprises a stable cyclopropenium cation thatremains positively charged at a high pH.

BRIEF DESCRIPTION OF THE DRAWINGS

The patent or application file contains at least one drawing executed incolor. Copies of this patent or patent application publication withcolor drawing(s) will be provided by the Office upon request and paymentof the necessary fee.

FIG. 1 shows a schematic representation of clicking the cyclopropeniumgroups onto a preformed polymer.

FIG. 2 shows a schematic representation of forming dendrimers fromtri-functional monomers.

FIG. 3 shows an image of a cross-linked polymer made according to thepresent invention.

FIG. 4 shows schematic structures of CP ion building blocks. (a)Structure of the CP ion, including the dialkylamino groups that can beused to stabilize and vary the application of this diverse buildingblock. (b) Types of polyelectrolytes that can be synthesized from CPmonomers by reversible-deactivation radical polymerization (RDRP)strategies and emulsion polymerization.

FIG. 5 shows a representative synthesis of CP monomers for RAFTpolymerisations according to the present invention. The monomers CPCyand CPiP were synthesized by addition of dicyclohexylamine (92%) anddiisopropylamine (85%) to 1, followed by substitution of styrenic-typeamine 5 under basic conditions (86% and 88%, respectively). CPMo wassimilarly synthesized. After addition of morpholine to 1, subsequenthydrolysis and treatment with oxalyl chloride (42%, 3 steps), 5 wassubstituted to yield CPMo (59%).

FIG. 6 shows a representative synthesis of CP-containing polymersaccording to the present invention. CPR is polymerized by RAFT yieldingboth homopolymers, PCPR, and statistical copolymers, P(S-stat-CPR). PCPRis reacted further to form block copolymers PS-b-PCPR of varying styrenecontent. Nanoparticles are synthesized by surfactant-free emulsionpolymerization with styrene using the water-soluble thermal initiatorV-50.

FIG. 7 shows a size exclusion chromatography (SEC) trace of PCPMo. Thedispersity (Ð) was found to be 1.3 (see Table 2).

FIG. 8 shows particles synthesized by surfactant-free emulsionpolymerization. Scanning electron microscopy (SEM) images and dynamiclight scattering (DLS) histograms, respectively, for 1 wt. % CPiP (a,d), 5 wt. % CPiP (b, e) and 0 wt. % CPiP (PS only) (c, f). Plot of zetapotential at a range of pH values for 5 wt. % CPiP (g).

FIG. 9 shows small angle X-ray scattering (SAXS) profiles of microphaseseparated diblock copolymers according to the present inventioncollected at 25° C. Scattering intensity is plotted as a function of themagnitude of the scattering vector, q. Filled triangles represent theprimary scattering peaks and the open triangles represent thehigher-order scattering peaks.

FIG. 10 shows representative SAXS profiles of microphase segregateddiblock copolymers according to the present invention collected at 25°C. Scattering intensity is plotted as a function of the magnitude of thescattering vector, q. Filled triangles represent the primary scatteringpeaks, and the open triangles represent the higher order scatteringpeaks.

FIG. 11 shows the morphology and ionic conductivity of bulk PS-b-PCPiPfilms. (a and b) Two representative TEM images of PS-b-PCPiP(20) reveala morphology of hexagonally packed cylinders (d-spacing=29 nm; the lightcolor corresponds to PS). (c) Ionic conductivity as a function ofinverse temperature, from 25 to 65° C., for (d) PS-b-PCPiP(20)(ion-exchange capacity, IEC=1.3, at 90% RH).

FIG. 12 shows transmission electron microscopy (TEM) images ofPS-b-PCPiP(20) without exposure to RuO₄ vapor. (a.) Cross-section of thecylinders. (b.) Hexagonally packed cylinders orientated orthogonal tothe section.

FIG. 13 shows a representative ¹H-NMR spectrum ofN-methyl-1-(2,3-bis(dicyclohexylamino)cyclopropenium)-4-vinylbenzylaminechloride (CPCy).

FIG. 14 shows a representative ¹³C NMR spectrum ofN-methyl-1-(2,3-bis(dicyclohexylamino)cyclopropenium)-4-vinylbenzylaminechloride (CPCy).

FIG. 15 shows a representative ¹H NMR spectrum ofN-methyl-1-(2,3-bis(diisopropylamino)cyclopropenium)-4-vinylbenzylaminechloride (CPiP).

FIG. 16 shows a representative ¹³C NMR spectrum ofN-methyl-1-(2,3-bis(diisopropylamino)cyclopropenium)-4-vinylbenzylaminechloride (CPiP).

FIG. 17 shows a representative ¹H NMR spectrum ofN-methyl-1-(2,3-bis(morpholino)cyclopropenium)-4-vinylbenzylaminechloride (CPMo).

FIG. 18 shows a representative ¹³C NMR spectrum ofN-methyl-1-(2,3-bis(morpholino)cyclopropenium)-4-vinylbenzylaminechloride (CPMo).

FIG. 19 shows a representative ¹H NMR spectrum of PCPCy.

FIG. 20 shows a representative ¹H NMR spectrum of PCPiP.

FIG. 21 shows a representative ¹H NMR spectrum of PCPMo.

DETAILED DESCRIPTION OF THE INVENTION

One embodiment of the present invention is a process for incorporating acyclopropenium ion into a polymeric system. This process comprisescontacting a functionalized cyclopropenium ion with a functionalizedcompound capable of reacting with the functional group of thecyclopropenium ion for a period of time and under conditions suitablefor the functionalized cyclopropenium and the functionalized compound toreact and form a polymeric system that comprises a stable cyclopropeniumcation that remains positively charged at a high pH.

In the present invention “incorporating” means to reset and form a bondbetween, e.g., a cyclopropenium ion and a preformed or currently formingpolymeric system. Preferably, the bond formed between the cyclopropeniumand the polymeric system is covalent.

As used herein, the term “cyclopropenium ion” means a charged speciesderived from a cyclopropene having the structure:

Derivatives of cyclopropenes, such as tetrachlorocyclopropene, arecommercially available from e.g., Sigma Aldrich (St. Louis, Mo.). As isalso known, cyclopropenium ions are highly geometrically strained, butthey are stabilized due to aromaticity. Various methods for makingcyclopropenium ions are also known. See, e.g., Wilcox et al., 1980;Yoshida, 1973.

In one aspect of the present embodiment, the polymeric system may be anypolymer containing agents into which a stable cyclopropenium cation thatremains positively charged at a high pH may be integrated. As usedherein, a “polymeric system” means a macromolecule having repeatingsub-units that are connected by covalent bonds. Non-limiting examples ofpolymeric systems include linear polymers, branched polymers,cross-linked polymers, and dendritic polymers. “Linear polymers” meanpolymers whose subunits are arranged in a linear chain. “Branchedpolymers” mean polymers whose chains have branching points that connecttwo or more chain segments. Branching generally occurs by thereplacement of a substituent, e.g., a hydrogen atom, on a monomersubunit, by another covalently bonded chain of that polymer or by achain of another type. “Cross-linked polymers” mean branched polymers inwhich adjacent long chains are joined to one and another at variouspositions along their lengths. The cross-linking creates greaterrigidity and stability. “Dendritic polymers” or “dendrimers” mean apolymer having a polyvalent core that is covalently bonded to at leasttwo ordered dendritic (tree-like) branches which extend through at leasttwo generations. Dendrimers thus have a starburst structure. As anexemplary illustration only, an ordered second generation dendriticbranch is depicted by the following configuration:

wherein “a” represents the first generation and “b” represents thesecond generation. An ordered, third generation dendritic branch may bedepicted by the following exemplary configuration:

wherein “a” and “b” represent the first and second generation,respectively, and “c” represents the third generation. A primarycharacteristic of the ordered dendritic branch which distinguishes itfrom conventional branches of conventional polymers is the uniform oressentially symmetrical character of the branches as is shown in theforegoing exemplary illustrations. In addition, with each newgeneration, the number of terminal groups on the dendritic branch is anexact multiple of the number of terminal groups in the previousgeneration. In the present invention, the number of generations isunlimited. Preferably, however, there are from about 1-1,000generations, such as from about 1-500, 1-250, 1-100, 1-50, 1-25, 1-15,1-10, 1-5, including 1-3 generations. The number of generations will bedetermined based on the particular end use of the final product.

As used herein, the term “functionalized” with reference to thecyclopropenium ion and the compound means possessing a functional group,which is an atom, or a group of atoms that has similar chemicalproperties whenever it occurs in different compounds. The respectivefunctional groups, under certain suitable conditions defined herein,react to form the polymeric system.

Functional groups include without limitation, alkoxy, alkoxycarbonyl,alkyl, alkenyl, alkenyloxy, alkenylthio, alkylamino, alkylsulfinyl,alkylsulfonyl, alkylthio, alkynyloxy, alkynylthio, amino, amido, aryl,aryloxy, aryl-alkyl, aryl-heteroalkyl, azide, carbocycle, carbonyl,carboxy, carboxylate, cyano, cycloalkyl, cycloalkenyl, ether, halo,heteroaryl, heteroaryloxy, heteroaryl-alkyl, heteroaryl-heteroalkyl,heteroalkyl, heteroaromatic, heterocycle, hydrocarbyl, hydroxyalkyl,hydroxyl, imino, nitro, polycycle, oxo, sulfate, sulfinyl, sulfonyl,thiol, thioalkyl, and thiono groups.

As used herein, conditions “suitable” for the functionalizedcyclopropenium and the functionalized compound to react and form apolymeric system are as exemplified herein and may also include thoseconditions disclosed by, e.g., Campos, 2008a and Campos 2008b.Parameters that may be varied to achieve such “suitable” conditionsinclude the concentration of the reactants, the duration of thereaction, the temperature of the reaction, the selection/use ofsolvent(s), and other reagents for isolating or otherwise purifying theproducts. Non-limiting exemplary “conditions suitable” for this processare disclosed, e.g., in the Examples herein and may be further apparentto those skilled in the art in view of the disclosures herein.

In the present invention, a “stable” cyclopropenium cation means acyclopropenium group with a positive charge that is not particularlyreactive under anticipated conditions of use, and retains its usefulproperties on the timescale of its expected usefulness. For example, astable cyclopropenium cation would not undergo ring opening reactionsunder normal conditions.

In the present invention, the polymeric system formed by contacting afunctionalized cyclopropenium ion with a functionalized compoundincludes a stable cyclopropenium cation that is positively chargedpreferably over a large pH range such as, e.g., from 0 to greater than14. Preferably, such cyclopropenium cation remains positively charged ata high pH, such as, e.g., a pH above 7, such as 7.5, 8, 8.5, 9, 9.5, 10,10.5, 11, 11.5, 12, 12.5, 13, 13.5, or 14. More preferably, thecyclopropenium cation incorporated into the polymeric system remainspositively charged in a pH range from 8 to 13.

In another aspect of this embodiment, the functionalized cyclopropeniumion is a compound of formula (100):

whereinX₁₋₃ are independently selected from the group consisting of Cl, N andany other atoms suitable for participating in the process; andR₁₄ are independently selected from the group consisting of no atom,amino, aryl, heteroaryl, C₁₋₁₀alkoxy, C₂₋₁₀alkenyloxy, C₂₋₁₀alkynyloxy,C₁₋₁₀alkyl, C₃₋₁₀cycloalkyl, C₂₋₁₀alkenyl, C₃₋₁₀cycloalkenyl,C₂₋₁₀alkynyl, halogen, aryloxy, heteroaryloxy, C₂₋₁₀alkoxycarbonyl,C₁₋₁₀alkylthio, C₂₋₁₀alkenylthio, C₂₋₁₀alkynylthio, C₁₋₁₀alkylsulfonyl,C₁₋₁₀alkylsulfinyl, aryl-C₁₋₁₀alkyl, heteroaryl-C₁₋₁₀alkyl,aryl-C₁₋₁₀heteroalkyl, heteroaryl-C₁₋₁₀heteroalkyl, a phosphorus group,a silicon group and a boron group, wherein R₁ and R₂ or R₃ and R₄ areoptionally combined to form a 5 to 8-membered carbocyclic orheterocyclic ring; further wherein the aliphatic or aromatic portions ofR₁ and R₂ are optionally substituted with from 1 to 4 substituentsselected from the group consisting of halogen, cyano, nitro, C₁₋₄alkyl,C₂₋₆alkenyl, C₂₋₆alkynyl, aryl, C₁₋₆alkoxy, C₂₋₆alkenyloxy,C₂₋₆alkynyloxy, aryloxy, C₂₋₆alkoxycarbonyl, C₁₋₆alkylthio,C₁₋₆alkylsulfonyl, C₁₋₆alkylsulfinyl, oxo, imino, thiono, primary amino,carboxyl, C₁₋₆alkylamino, C₁₋₆dialkylamino, amido, nitrogenheterocycles, hydroxy, thiol and phosphorus.

As used herein, atoms “suitable for participating in the process” meansatoms that do not interfere with the incorporation of a cyclopropeniumion into a polymeric system. Besides N and Cl, non-limiting examples ofother atoms that are suitable for participating in the process mayinclude halogens such as F, Br, and I.

Preferably, the functionalized cyclopropenium ion is selected from thegroup consisting of:

optionally together with an appropriate counter ion. Such counter ionsmay be any negatively charged ion, including without limitation,chloride, bicarbonate, phosphate, and sulfate ions.

In another preferred embodiment, the functionalized cyclopropenium ionis selected from the group consisting of:

whereinR₁₋₄ are independently selected from the group consisting of

and combinations thereof.

In yet another preferred embodiment, the functionalized cyclopropeniumion is selected from the group consisting of:

whereinR₁₋₄ are independently selected from the group consisting of

wherein R is any group that is suitable for participating in the processof incorporating the cyclopropenium ion into the polymeric system; andcombinations thereof.

As used herein, a group that is “suitable for participating in theprocess of incorporating the cyclopropenium ion into the polymericsystem” is any chemical group that can be stably attached to thecyclopropenium ion in the polymeric system. Such suitable groups areselected from moieties that are not overly bulky, such as, e.g.,hydrogen and methyl, so as to minimize crowding around thecyclopropenium ion.

In yet another preferred embodiment, the functionalized cyclopropeniumion is:

In an additional preferred embodiment, the functionalized cyclopropeniumion is:

In a further preferred embodiment, the functionalized cyclopropenium ionis:

In another preferred embodiment, the functionalized cyclopropenium ionis:

In a further aspect of this embodiment, the functionalized compoundcapable of reacting with the functional group of the cyclopropenium ionis a polymer selected from the group consisting of a linear polymer, abranched polymer, a cross-linked polymer, and a dendritic polymer.Preferably, the polymer is a homopolymer or a heteropolymer. As usedherein, a “homopolymer” is a polymer that contains only a single type ofrepeating sub-unit. A “heteropolymer” or “copolymer” is a polymercontaining a mixture of repeating sub-units. Heteropolymers includerandom copolymers, block copolymers, and graft copolymers.

As used herein, a “random copolymer” means a copolymer in which theprobability of finding a given monomeric unit at any given site in thechain is independent of the nature of the adjacent units.

As used herein, a “block copolymer” means a copolymer containing blocksor segments of different polymerized monomers.

As used herein, a “graft copolymer” means a copolymer with one or morespecies of segments connected to the backbone as side chains, these sidechains having different composition or sequence distribution from thebackbone. The term “backbone” as used herein refers to that portion ofthe polymer which is a continuous chain. The term “side chain” refers toportions of the polymer that append from the backbone.

In another aspect of this embodiment, the backbone of the polymercomprises a group selected from the group consisting of ethylene,propylene, styrene, (meth)acrylate, vinyl chloride, urethane, ethyleneterephthalate, ester, amide, norbornene, silicon, oxygen, andcombinations thereof.

In another aspect of this embodiment the functionalized cyclopropeniumion is a compound of formula (100):

whereinX₁₋₃ are independently selected from the group consisting of Cl, N, andany other atom suitable for participating in the process; andR₁₄ are independently selected from the group consisting of no atom,amino, aryl, heteroaryl, C₁₋₁₀alkoxy, C₂₋₁₀alkenyloxy, C₂₋₁₀alkynyloxy,C₁₋₁₀alkyl, C₃₋₁₀cycloalkyl, C₂₋₁₀alkenyl, C₃₋₁₀cycloalkenyl,C₂₋₁₀alkynyl, halogen, aryloxy, heteroaryloxy, C₂₋₁₀alkoxycarbonyl,C₁₋₁₀alkylthio, C₂₋₁₀alkenylthio, C₂₋₁₀alkynylthio, C₁₋₁₀alkylsulfonyl,C₁₋₁₀alkylsulfinyl aryl-C₁₋₁₀alkyl, heteroaryl-C₁₋₁₀alkyl,C₁₋₁₀alkyl-aryl-C₂₋₆alkenyl, aryl-C₁₋₁₀heteroalkyl,heteroaryl-C₁₋₁₀heteroalkyl, a phosphorus group, a silicon group and aboron group, wherein R₁ and R₂ or R₃ and R₄ are optionally combined toform a 5 to 8-membered carbocyclic or heterocyclic ring; further whereinthe aliphatic or aromatic portions of R₁ and R₂ are optionallysubstituted with from 1 to 4 substituents selected from the groupconsisting of halogen, cyano, nitro, C₁₋₄alkyl, C₂₋₆alkenyl,C₂₋₆alkynyl, aryl, C₁₋₆alkoxy, C₂₋₆alkenyloxy, C₂₋₆alkynyloxy, aryloxy,C₂₋₆alkoxycarbonyl, C₁₋₆alkylthio, C₁₋₆alkylsulfonyl, C₁₋₆alkylsulfinyl,oxo, imino, thiono, primary amino, carboxyl, C₁₋₆alkylamino,C₁₋₆dialkylamino, amido, nitrogen heterocycles, hydroxy, thiol andphosphorus.

In a further aspect of this embodiment the functionalized cyclopropeniumion is selected from the group consisting of:

whereinR₁ and R₂ are independently selected from the group consisting of

wherein R₁ and R₂ are optionally combined to form

and combinations thereof.

In a preferred aspect of this embodiment the functionalizedcyclopropenium ion is selected from the group consisting of:

In another preferred aspect of this embodiment, the process is carriedout according to a process selected from the following:

a)

b)

c)

Another embodiment of the present invention is a stable, polycationiccompound made by a process of the invention.

Another embodiment of the present invention is a substrate comprising acompound of the invention.

Another embodiment of the present invention is a support coated with asubstrate of the invention for use in an electronic device.

Another embodiment of the present invention is a process for making across-linked polymer. This process comprises contacting an alkenefunctionalized cyclopropenium ion with a polymer comprising a pendantthiol group, for a period of time and under conditions suitable for thefunctionalized cyclopropenium ion and the polymer to react and form across-linked polymer that comprises a stable cyclopropenium cation thatremains positively charged at a high pH.

In one aspect of this embodiment, the process is carried out accordingto the following reaction:

In this reaction, n may be any integer. Preferably, n is from 1 to 10¹⁰,such as from 1 to 10⁷, 1 to 10⁵, 1 to 1000, 1 to 500, 1 to 50, and 1 to10. Selection of the size of the polymer will be driven by the desiredfunctions of the cross-linked polymer.

The initiator in this reaction is preferably, a radical initiator thatis activated by heat or light, such as, e.g., phenylacetophenone (DMPA),azobisisobutyronitrile (AIBN), 4,4′-azobis(4-cyanovaleric acid),1,1′-azobis(cyclohexanecarbonitrile),2-benzyl-2-(dimethylamino)-4′-morpholinobutyrophenone,4′-tert-butyl-2′,6′-dimethylacetophenone, 2,2-diethoxyacetophenone,2,2-dimethoxy-2-phenylacetophenone,diphenyl(2,4,6-trimethylbenzoyl)phosphineoxide/2-hydroxy-2-methylpropiophenone, 4′-ethoxyacetophenone,3′-hydroxyacetophenone, 4′-hydroxyacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-4′-(2-hydroxyethoxy)-2-methylpropiophenone,2-hydroxy-2-methylpropiophenone,2-methyl-4′-(methylthio)-2-morpholinopropiophenone,4′-phenoxyacetophenone, benzoin, 4,4′-dimethoxybenzoin,4,4′-dimethylbenzil, benzophenone-3,3′,4,4′-tetracarboxylic dianhydride,4-benzoylbiphenyl, 4,4′-bis(diethylamino)benzophenone,4,4′-bis[2-(1-propenyl)phenoxy]benzophenone,4-(diethylamino)benzophenone, 4,4′-dihydroxybenzophenone,4-(dimethylamino)benzophenone, 3,4-dimethylbenzophenone,3-hydroxybenzophenone, 4-hydroxybenzophenone, 2-methylbenzophenone,3-methylbenzophenone, 4-methylbenzophenone, methyl benzoylformate,michler's ketone, bis(4-tert-butylphenyl)iodoniumperfluoro-1-butanesulfonate, bis(4-tert-butylphenyl)iodoniump-toluenesulfonate, bis(4-tert-butylphenyl)iodonium triflate,boc-methoxyphenyldiphenylsulfonium triflate,(4-bromophenyl)diphenylsulfonium triflate,(tert-butoxycarbonylmethoxynaphthyl)-diphenylsulfonium triflate,(4-tert-butylphenyl)diphenylsulfonium triflate, diphenyliodoniumhexafluorophosphate, diphenyliodonium nitrate, diphenyliodoniumperfluoro-1-butanesulfonate, diphenyliodonium p-toluenesulfonate,diphenyliodonium triflate, (4-fluorophenyl)diphenylsulfonium triflate,n-hydroxynaphthalimide triflate,n-hydroxy-5-norbornene-2,3-dicarboximide perfluoro-1-butanesulfonate,(4-iodophenyl)diphenylsulfonium triflate,(4-methoxyphenyl)diphenylsulfonium triflate,2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine,(4-methylphenyl)diphenylsulfonium triflate, (4-methylthiophenyl)methylphenyl sulfonium triflate, 1-naphthyl diphenylsulfonium triflate,(4-phenoxyphenyl)diphenylsulfonium triflate,(4-phenylthiophenyl)diphenylsulfonium triflate, triarylsulfoniumhexafluoroantimonate, triarylsulfonium hexafluorophosphate,triphenylsulfonium perfluoro-1-butanesufonate, triphenylsulfoniumtriflate, tris(4-tert-butylphenyl)sulfonium perfluoro-1-butanesulfonate,tris(4-tert-butylphenyl)sulfonium triflate,1-chloro-4-propoxy-9h-thioxanthen-9-one, 2-chlorothioxanthen-9-one,2,4-diethyl-9h-thioxanthen-9-one, isopropyl-9h-thioxanthen-9-one,10-methylphenothiazine, thioxanthen-9-one, persulfate, tert-butylhydroperoxide, tert-butyl peracetate, cumene hydroperoxide,2,5-di(tert-butylperoxy)-2,5-dimethyl-3-hexyne, dicumyl peroxide,2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, 2,4-pentanedione peroxide,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane,1,1-bis(tert-butylperoxy)cyclohexane,1,1-bis(tert-amylperoxy)cyclohexane, benzoyl peroxide, 2-butanoneperoxide, tert-butyl peroxide, di-tert-amyl peroxide, lauroyl peroxide,tert-butyl peroxybenzoate, tert-butylperoxy 2-ethylhexyl carbonate,tert-butyl hydroperoxide, and lithiumphenyl-2,4,6-trimethylbenzoylphosphinate (LAP) (Fairbanks et al., 2009).

Yet another embodiment of the present invention is a process for makinga cross-linked polymer. This process comprises contacting a thiolfunctionalized cyclopropenium ion with a functionalized compoundcomprising an alkene group, for a period of time and under conditionssuitable for the functionalized cyclopropenium ion and thefunctionalized compound to react and form a cross-linked polymer thatcomprises a stable cyclopropenium cation that remains positively chargedat a high pH.

In one aspect of this embodiment, the process is carried out accordingto the following reaction:

In this embodiment, “n”, “initiator”, and “polymer” are as disclosedabove.

Another embodiment of the present invention is a process for making alinear polymer. This process comprises contacting a functionalizedcyclopropenium ion with a polymerizing agent for a period of time andunder conditions suitable for the functionalized cyclopropenium ion toreact and to form a linear polymer that comprises a stablecyclopropenium cation that remains positively charged at a high pH.

In this embodiment, a “polymerizing agent” is a substance thatfacilitates the formation of covalent bonds among monomers to formpolymers. Polymerizing agents include radical initiators, ReversibleAddition-Fragmentation chain Transfer (RAFT) agents, and catalysts forclick chemistry. Radical initiators are as disclosed above. RAFT agentsinclude without limitation,

pentamethyldiethylenetriamine (PMDETA), dithioesters, dithiocarbamates,trithiocarbonates, and xanthates. Catalysts for click chemistry includewithout limitation Cu(I).

In one aspect of this embodiment, the process further comprisescontacting the functionalized cyclopropenium ion with a monomer suitablefor forming a copolymer with the functionalized cyclopropenium ion. Inthe present invention, a suitable monomer is one that will not interferewith the reaction in a substantive way and that provides a desiredattribute as a part of the copolymer. Representative non-limitingexamples of a suitable monomer in this reaction include vinyl monomers,pyrolyzates, alcohols, phenols, carboxylic acids, and their salts,esters, anhydrides, amides, hydrazides, urethanes, cyanates, fulminates,heterocycles, amino, and thiocarboxylic acids, and sulphonamides.

In another aspect of this embodiment, the process is carried outaccording to the following reaction:

wherein

is any suitable polymer backbone;X₁₋₃ are independently selected from the group consisting of Cl, N, andany other atom suitable for participating in the process;R₁₋₄ are independently selected from the group consisting of no atom,amino, aryl, heteroaryl, C₁₋₁₀alkoxy, C₂₋₁₀alkenyloxy, C₂₋₁₀alkynyloxy,C₁₋₁₀alkyl, C₃₋₁₀cycloalkyl, C₂₋₁₀alkenyl, C₃₋₁₀cycloalkenyl,C₂₋₁₀alkynyl, halogen, aryloxy, heteroaryloxy, C₂₋₁₀alkoxycarbonyl,C₁₋₁₀alkylthio, C₂₋₁₀alkenylthio, C₂₋₁₀alkynylthio, C₁₋₁₀alkylsulfonyl,C₁₋₁₀alkylsulfinyl, aryl-C₁₋₁₀alkyl, heteroaryl-C₁₋₁₀alkyl,aryl-C₁₋₁₀heteroalkyl, heteroaryl-C₁₋₁₀heteroalkyl, a phosphorus group,a silicon group and a boron group, wherein R₁ and R₂ or R₃ and R₄ areoptionally combined to form a 5 to 8-membered carbocyclic orheterocyclic ring; further wherein the aliphatic or aromatic portions ofR₁ and R₂ are optionally substituted with from 1 to 4 substituentsselected from the group consisting of halogen, cyano, nitro, C₁₋₄alkyl,C₂₋₆alkenyl, C₂₋₆alkynyl, aryl, C₁₋₆alkoxy, C₂₋₆alkenyloxy,C₂₋₆alkynyloxy, aryloxy, C₂₋₆alkoxycarbonyl, C₁₋₆alkylthio,C₁₋₆alkylsulfonyl, C₁₋₆alkylsulfinyl, oxo, imino, thiono, primary amino,carboxyl, C₁₋₆alkylamino, C₁₋₆dialkylamino, amido, nitrogenheterocycles, hydroxy, thiol and phosphorus, wherein one of R₃ or R₄ isa group that forms a polymer backbone when contacted with thepolymerizing agent; andA is selected from the group consisting of:

The polymerizing agent is as disclosed above. Preferably, thepolymerizing agent is DMPA or AIBN.

In this aspect of the present invention, the length of the polymerbackbone is not critical and is readily determined and/or modifiedaccording to the end use of the linear polymer. Thus n may be anypositive integer. For example, n may vary between 1-1,000,000, such as1-500,000, or 1-250,000, or 1-100,000, or 1-50,000, or 1-25,000, or1-10,000, or 1-1,000, or 1-500, or 1-250, or 1-100, or 1-50, or 1-25, or1-10, or 1-5.

Preferably, the backbone of the polymer is selected from the groupconsisting of polymers based on styrene, (meth)acrylate, norbornene, andcombinations thereof.

In another preferred embodiment, R₁ and R₂ are independently selectedfrom the group consisting of:

combinations thereof.

In an additional preferred embodiment, X₃R₃R₄ is selected from the groupconsisting of:

and combinations thereof.

An additional embodiment of the present invention is a process forincorporating a cyclopropenium ion onto a preformed polymer. Thisprocess comprises contacting a cyclopropenium ion functionalized toparticipate in a click reaction with a preformed polymer backbone havinga pendant group that is functionalized with a complementary groupsuitable for participating in a click reaction with the cyclopropeniumion for a period of time and under conditions suitable for thefunctionalized cyclopropenium ion and the preformed polymer to react viaa click chemistry mechanism and form a polymer that comprises a stablecyclopropenium cation that remains positively charged at a high pH.

In the present invention, a “preformed polymer” is intended to includeany polymer suitable for participating in a click chemistry reactionwith a suitably functionalized cyclopropenium ion as disclosed in moredetail herein. Typically, the polymer is formed prior to the clickreaction. The preformed polymer contains one or more pendant groups,which are able to react in a click chemistry reaction with thefunctionalized cyclopropenium as set forth in more detail below.Non-limiting examples of functionalized groups for the cyclopropeniumion and the preformed polymers are alkynes, azides, thiols, enes,epoxides, aziridines, aziridinium ions, aldehydes, and aminooxy groups.

The reaction time and conditions for the click chemistry will depend onthe particular functional groups used and other desired properties andare well within the skill of the art to determine. Representativenon-limiting reaction times and conditions are set forth in more detailbelow and in the Examples.

As used herein, a “click” reaction means a chemical reaction in whichsmall modular components are joined together to form a larger molecule,are easy to perform, and give rise to their intended products in veryhigh yields with little or no byproducts. Many click components arederived from alkenes and alkynes, and most click reactions involve theformation of carbon-heteroatom (mostly N, O, and S) bonds. Clickreactions are usually fusion processes (leaving no byproducts) orcondensation processes (producing water as a byproduct).

Perhaps the most famous of click reactions is the Huisgen 1,3-dipolarcycloaddition of alkynes and azides to yield 1,2,3-triazoles, whichreaction is accelerated by copper(I) catalysis (Kolb et al., 2001). Thisreaction requires no protecting groups, and proceeds with extremely highyield and selectivity for the 1,4-disubstituted 1,2,3-triazole(anti-1,2,3-triazole). For a detailed review of the mechanistic aspectsof this reaction, see, e.g., Bock et al., 2006.

Another example of a click reaction is the thiol-ene reaction involvingthe addition of a S—H bond across a double or triple bond by either afree radical or ionic mechanism. The reaction product is an alkenylsulfide. For a review, see, e.g., Hoyle et al., 2010.

Other non-limiting examples of click reactions include nucleophilic ringopening reactions, such as the opening of epoxides, aziridines, andaziridinium ions; non-aldol carbonyl chemistry, such as the formation ofureas, oximes and hydrazones; additions to carbon-carbon multiple bonds,especially oxidative addition, Michael additions of Nu-H reactants; andcycloaddition reactions, especially the Diels-Alder reaction (Lee etal., 2003; Lewis et al., 2002; Rostovtsev, 2002; Black et al., 2008,Devaraj et al., 2008, Stockmann et al., 2011, Tornoe et al., 2002, Borenet al., 2008, McNulty et al., 2011; Himo et al., 2005; Moses et al.,2007; U.S. Pat. No. 7,375,234; US Patent Publication NOs. 2011/0077365and 2010/0197871).

In one aspect of this embodiment, the reaction is carried out accordingto:

whereinB represents a pendant group that comprises a group suitable forparticipating in a click reaction with the cyclopropenium ion;

is selected from the group consisting of:

R₁₋₂ are independently selected from the group consisting of no atom,amino, aryl, heteroaryl, C₁₋₁₀alkoxy, C₂₋₁₀alkenyloxy, C₂₋₁₀alkynyloxy,C₁₋₁₀alkyl, C₃₋₁₀cycloalkyl, C₂₋₁₀alkenyl, C₃₋₁₀cycloalkenyl,C₂₋₁₀alkynyl, halogen, aryloxy, heteroaryloxy, C₂₋₁₀alkoxycarbonyl,C₁₋₁₀alkylthio, C₂₋₁₀alkenylthio, C₂₋₁₀alkynylthio, C₁₋₁₀alkylsulfonyl,C₁₋₁₀alkylsulfinyl, aryl-C₁₋₁₀alkyl, heteroaryl-C₁₋₁₀alkyl,aryl-C₁₋₁₀heteroalkyl, heteroaryl-C₁₋₁₀heteroalkyl, a phosphorus group,a silicon group and a boron group, wherein R₁ and R₂ are optionallycombined to form a 5 to 8-membered carbocyclic or heterocyclic ring;further wherein the aliphatic or aromatic portions of R₁ and R₂ areoptionally substituted with from 1 to 4 substituents selected from thegroup consisting of halogen, cyano, nitro, C₁₋₄alkyl, C₂₋₆alkenyl,C₂₋₆alkynyl, aryl, C₁₋₆alkoxy, C₂₋₆alkenyloxy, C₂₋₆alkynyloxy, aryloxy,C₂₋₆alkoxycarbonyl, C₁₋₆alkylthio, C₁₋₆alkylsulfonyl, C₁₋₆alkylsulfinyl,oxo, imino, thiono, primary amino, carboxyl, C₁₋₆alkylamino,C₁₋₆dialkylamino, amido, nitrogen heterocycles, hydroxy, thiol andphosphorus; andC represents the linkage formed between the cyclopropenium ion and thepolymer. Typically, the linkage, C, includes a covalent linkage.

Preferably, R₁ and R₂ are independently selected from the groupconsisting of:

and combinations thereof.

Another embodiment of the present invention is a process for making adendritic polymer. This process comprises the steps of:

a. providing a first functionalized compound comprising a cyclopropeniumion, which has a reactive group at each position of the ring; and

b. grafting a second functionalized compound onto each reactive group ofthe first functionalized compound such that chemical bonds are formedbetween the first functionalized compound and the second functionalizedcompound at the reactive groups, the second functionalized compoundincluding reactive groups capable of forming bonds with the reactivegroups on the cyclopropenium ion, and wherein the bonds are formedthrough a click chemistry mechanism.

The first and second compounds include any compound or polymer that willnot prevent or substantially interfere in the click chemistry reaction.Selection of the particular first and second compounds is within theskill of the art and will be driven by the particular properties desiredof the dendritic polymer. Non-limiting examples of the first and secondcompounds include the following:

As set forth above, the reactive groups on the respective first andsecond compounds are suitable for participation in click chemistry.Preferred reactive groups include without limitation azide, alkynyl,alkenyl, and thiol.

In one aspect of this embodiment, the first functionalized compound andthe second functionalized compound are independently selected from ahomopolymer or a copolymer, and are further independently selected fromlinear, branched, or dendritic polymers.

In another aspect of this embodiment, both the first and the secondfunctionalized compounds comprise a cyclopropenium ion.

In yet another aspect of this embodiment, the first functionalizedcompound is:

In a further aspect of this embodiment, the second functionalizedcompound is selected from:

In yet another aspect of this embodiment, the reactive groups arelocated at a terminal position on the second functionalized compound.

In an additional aspect of this embodiment, a cycle defined by steps (a)and (b) is repeated at least once, such as 2, 3, 4, 5, 6, 7, 8, 9, 10,12, 15, 20 or more times, and the polymer formed at step (b) of thepreceding cycle is a substrate for the providing step (a) in thesubsequent cycle. Preferably, the cycle is repeated from 1 to 6 times.

An additional embodiment of the present invention is a stable,polycationic compound made by any process disclosed herein.

A further embodiment of the present invention is a polymer thatcomprises a stable cyclopropenium cation that remains positively chargedat a high pH. The polymer has the structure:

whereinX₁₋₂ are independently selected from the group consisting of Cl, N, andany other atom suitable for participating in the process;R₁₋₂ are independently selected from the group consisting of no atom,amino, aryl, heteroaryl, C₁₋₁₀alkoxy, C₂₋₁₀alkenyloxy, C₂₋₁₀alkynyloxy,C₁₋₁₀alkyl, C₃₋₁₀cycloalkyl, C₂₋₁₀alkenyl, C₃₋₁₀cycloalkenyl,C₂₋₁₀alkynyl, halogen, aryloxy, heteroaryloxy, C₂₋₁₀alkoxycarbonyl,C₁₋₁₀alkylthio, C₂₋₁₀alkenylthio, C₂₋₁₀alkynylthio, C₁₋₁₀alkylsulfonyl,C₁₋₁₀alkylsulfinyl, aryl-C₁₋₁₀alkyl, heteroaryl-C₁₋₁₀alkyl,aryl-C₁₋₁₀heteroalkyl, heteroaryl-C₁₋₁₀heteroalkyl, a phosphorus group,a silicon group and a boron group, wherein R₁ and R₂ are optionallycombined to form a 5 to 8-membered carbocyclic or heterocyclic ring;further wherein the aliphatic or aromatic portions of R₁ and R₂ areoptionally substituted with from 1 to 4 substituents selected from thegroup consisting of halogen, cyano, nitro, C₁₋₄alkyl, C₂₋₆alkenyl,C₂₋₆alkynyl, aryl, C₁₋₆alkoxy, C₂₋₆alkenyloxy, C₂₋₆alkynyloxy, aryloxy,C₂₋₆alkoxycarbonyl, C₁₋₆alkylthio, C₁₋₆alkylsulfonyl, C₁₋₆alkylsulfinyl,oxo, imino, thiono, primary amino, carboxyl, C₁₋₆alkylamino,C₁₋₆dialkylamino, amido, nitrogen heterocycles, hydroxy, thiol andphosphorus;

represents a suitable linking group; andn is an integer.

In one aspect of this embodiment, the polymer is selected from the groupconsisting of a linear polymer, a branched polymer, a cross-linkedpolymer, and a dendritic polymer.

In another aspect of this embodiment, the polymer is a homopolymer or aheteropolymer. Suitable homopolymers and heteropolymers are as disclosedherein. Representative non-limiting examples of heteropolymers withinthe scope of the present invention include random copolymers, blockcopolymers, and graft copolymers.

In a further aspect of this embodiment, the polymer backbone is anysuitable polymeric backbone having useful properties in accordance withthe present invention. For example, the polymer backbone may be selectedfrom the group consisting of ethylene, propylene, styrene,(meth)acrylate, vinyl chloride, urethane, ethylene terephthalate, ester,amide, norbornene, silicon, oxygen, and combinations thereof.

Preferred pH ranges are as disclosed above.

In this embodiment of the present invention, the integer “n” is aspreviously defined.

A “suitable linking group” as used herein means a moiety that covalentlyconnects a cyclopropenium ion to the polymer backbone, which moiety doesnot render the polymer unstable by, e.g., reaction with R₁ or R₂ groups.Suitable linking groups include, without limitation, no atom,unsubstituted and substituted functional groups such as amino, aryl,heteroaryl, alkoxy, alkenyloxy, alkynyloxy, alkyl, cycloalkyl, alkenyl,cycloalkenyl, alkynyl, ether, halogen, aryloxy, heteroaryloxy,alkoxycarbonyl, alkylthio, alkenylthio, alkynylthio, alkylsulfonyl,alkylsulfinyl, aryl-alkyl, heteroaryl-alkyl, aryl-heteroalkyl,heteroaryl-heteroalkyl, a phosphorus group, a silicon group and a borongroup.

In another aspect of this embodiment, R₁₋₂ are independently selectedfrom the group consisting of

and combinations thereof.

In another aspect of this embodiment, R₁₋₂ are independently selectedfrom the group consisting of

and combinations thereof.

In a preferred aspect of this embodiment the polymer is

In an additional aspect of this embodiment, the polymer is selected fromthe group consisting of:

Another embodiment of the present invention is a cross-linked polymerthat comprises a stable cyclopropenium cation that remains positivelycharged at a high pH, the cross-linked polymer having the structure:

wherein

represents a suitable linking group; andpolymer is any polymer that can be bonded to the cyclopropenium ion.

In one aspect of this embodiment, the cross-linked polymer is selectedfrom the group consisting of:

wherein polymer is any polymer that can be bonded to the cyclopropeniumion. Suitable polymers include, e.g., those whose backbones compriseethylene, propylene, styrene, (meth)acrylate, vinyl chloride, urethane,ethylene terephthalate, ester, amide, norbornene, silicon, oxygen, orcombinations thereof.

An additional embodiment of the present invention is a dendrimer having(1) a cationic core comprising a tri-functional cyclopropenium monomerand (2) at least two ordered dendritic core branches which (a) arecovalently bonded to the cationic core, (b) extend through at least twogenerations, and (c) have at least 3 terminal groups per core branch.

In one aspect of this embodiment, the cationic core is:

In another aspect of this embodiment, the dendritic core branches areindependently selected from:

Another embodiment of the present invention is a process forincorporating a cyclopropenium ion into a polymeric system. This processcomprises contacting a functionalized cyclopropene with a functionalizedcompound capable of reacting with the functionalized cyclopropene for aperiod of time and under conditions suitable for the functionalizedcyclopropene and the functionalized compound to react and form apolymeric system that comprises a stable cyclopropenium cation thatremains positively charged at a high pH.

In one aspect of this embodiment, the functionalized cyclopropene is acompound of formula (200):

whereinX₁₋₃ are independently selected from the group consisting of Cl, N andany other atoms suitable for participating in the process; andR₁₋₄ are independently selected from the group consisting of no atom,amino, aryl, heteroaryl, C₁₋₁₀alkoxy, C₂₋₁₀alkenyloxy, C₂₋₁₀alkynyloxy,C₁₋₁₀alkyl, C₃-10cycloalkyl, C₂₋₁₀alkenyl, C₃₋₁₀cycloalkenyl,C₂₋₁₀alkynyl, halogen, aryloxy, heteroaryloxy, C₂₋₁₀alkoxycarbonyl,C₁₋₁₀alkylthio, C₂₋₁₀alkenylthio, C₂₋₁₀alkynylthio, C₁₋₁₀alkylsulfonyl,C₁₋₁₀alkylsulfinyl, aryl-C₁₋₁₀alkyl, heteroaryl-C₁₋₁₀alkyl,aryl-C₁₋₁₀heteroalkyl, heteroaryl-C₁₋₁₀heteroalkyl, a phosphorus group,a silicon group and a boron group, wherein R₁ and R₂ or R₃ and R₄ areoptionally combined to form a 5 to 8-membered carbocyclic orheterocyclic ring; further wherein the aliphatic or aromatic portions ofR₁ and R₂ are optionally substituted with from 1 to 4 substituentsselected from the group consisting of halogen, cyano, nitro, C₁₋₄alkyl,C₂₋₆alkenyl, C₂₋₆alkynyl, aryl, C₁₋₆alkoxy, C₂₋₆alkenyloxy,C₂₋₆alkynyloxy, aryloxy, C₂₋₆alkoxycarbonyl, C₁₋₆alkylthio,C₁₋₆alkylsulfonyl, C₁₋₆alkylsulfinyl, oxo, imino, thiono, primary amino,carboxyl, C₁₋₆alkylamino, C₁₋₆dialkylamino, amido, nitrogenheterocycles, hydroxy, thiol and phosphorus.

Preferably, the functionalized cyclopropene is:

In another preferred embodiment, X₁₋₂ are both N, and R₁₋₂ areindependently selected from the group consisting of C₁₋₆alkyl, aryl, andC₃₋₁₀cycloalkyl. More preferably, R₁₋₂ are both cyclohexyl.

In another aspect of this embodiment, the functionalized compoundcapable of reacting with the functional group of the functionalizedcyclopropene is a polymer selected from the group consisting of a linearpolymer, a branch polymer, a cross-linked polymer, and a dendriticpolymer.

Preferably, the polymer is a homopolymer or a heteropolymer. In onepreferred embodiment, the polymer is a homopolymer ofpoly(N-alkylamino)methylstyrene.

In another preferred embodiment, the polymer is a heteropolymer, such asa random copolymer or a block polymer. More preferably, the randomcopolymer is a copolymer of polystyrene andpoly(N-alkylamino)methylstyrene. Preferred block polymers includediblock copolymer, such as one that has the following structure:

whereinx, y, and z are independently selected from integers greater than orequal to zero, and R is any group that is suitable for participating inthe process of incorporating the cyclopropenium ion into the polymericsystem. x, y, and z may range from 0-1,000, including 0-500, 0-250,0-100, 0-50, 0-25, 0-10, and 0-5. For example, x, y, and z may beindependently selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10.

A stable, polycationic compound made by the process disclosed herein maybe self-assembling when contacted with a substrate. As used herein,“self-assembling” refers to a process in which molecules (includingmacromolecules such as polymers) form ordered structures, such asspheres, cylinders, lamellae, vesicles, as a consequence of interactionsamong the molecules themselves. Such ordered structures may be on thescale of nanometers, and thus, polymers, especially block polymers, aresuitable for different applications in various fields, such asbiomedicine, biomaterials, microelectronics, photoelectric materials,and catalysis. Self-assembly of polymers may further be directed bymodifying confinement conditions, surface of the substrate in contactwith the polymers (including graphoepitaxy and chemical registrationtechniques), and thermal and solvent annealing conditions. Such methodsare known in the art and are disclosed in e.g., Albert et al., 2010; Maiet al., 2012; and Takenaka et al., 2013.

A further embodiment of the present invention is a substrate. Thissubstrate comprises a stable, polycationic compound made by any processdisclosed herein. A “substrate” as used in this embodiment may take anyform convenient to the end use, such as, e.g., a film, a bead, a gel, amembrane, a coating, a powder, and the like. A non-limiting exemplarysubstrate made by the process disclosed herein is shown in FIG. 3.

Another embodiment of the present invention is a support coated with anysubstrate disclosed herein for use in a water purification system.

The support generally serves as a mechanical structure for the coatingsubstrate. The support may be made from the same polymer as the coatingmaterial or from one or more different polymers.

The support coated with one or more substrates disclosed herein may beused, inter alia, to adsorb contaminants, to disinfect (i.e., used as anantimicrobial), or for reverse osmosis (e.g., for desalination).

Methods of coating a support are known in the art and such methods maybe used to coat a support with a substrate according to the presentinvention. Such methods include, without limitation, spin-coating,dip-coating, interfacial polymerization, painting, spraying,electrophoretic deposition, tape casting, and Langmuir-Blodget coating,phase inversion (polymer precipitation), such as those disclosed ine.g., U.S. Pat. Nos. 4,728,576; 5,069,156; and 5,844,192; U.S. PatentPublication No. 2006/0049540; Krogman et al., 2009; Kesting, 1985;Cabasso, 1987; Strathmann, 1990. Multiple layers may be deposited usinglayer-by layer methods, such as those disclosed in e.g., Decher et al.,1997.

In currently available water purification systems, the purificationmembranes used typically lack tunable mechanical properties and can bebrittle. Furthermore, the chemistry for making such membranes isdifficult to manage due to the fact that typically, acid chlorides usedto make the membrane must be processed in dry conditions because uponcontact with water, acid chlorides reacts with water to form thecorresponding carboxylic acids. See, e.g., Porter, 1990. The newsubstrates disclosed herein can be used with a wide variety ofcross-linking units to tune the mechanical properties. Furthermore, thechemistry disclosed herein to make the water purification membrane canbe done at a bench top, in the presence of water, under ambientconditions, and in as little as a few seconds. Furthermore, thechemistry disclosed herein is versatile and may be used to makeantimicrobial coatings and substrates for cell cultures, as disclosed inmore detail below.

The chemistry disclosed herein is also modular. For example,functionalized cyclopropenium cations may be linked to any preformedpolymer with the corresponding functional group by click chemistry.Moreover, functionalized cyclopropenium cations may serve as dendriticcores, and various dendritic core branches may be added onto the cores.In addition, the cyclopropenium cation units can be obtained fromreadily available precursors and the chemistry is robust, efficient, anduser-friendly. Furthermore, it provides a new level of functionality inmaterials science, yielding a cationic species that can maintain itscharge at high pH.

Yet another embodiment of the present invention is an antimicrobialcoating comprising any substrate disclosed herein. The term“antimicrobial,” as used herein, means that the present coatingsinhibit, prevent, or destroy the growth or proliferation ofmicroorganisms, such as viruses, bacteria, and fungi.

Polymers bearing quaternary ammonium cations have antibacterialactivities. Furthermore, it has been shown that antibacterial activityincreased with the increase of the amount of quaternary ammonium groupsin the polymer (Kenawy et al., 2007). Other groups that may beincorporated into the antibacterial coatings of the present inventioninclude phosphonium and pyridinium groups. Therefore, it is expectedthat polymeric systems containing cyclopropenium cations as disclosedherein will have similar antibacterial activities. It is also expectedthat antibacterial activity will increase with the increase of theamount of cyclopropenium cations incorporated in the polymer.

In one aspect of this embodiment, a stable cationic dendritic polymermay be deposited onto electrospun sheets, beads coated on sutures, andon, e.g., dental restorative materials for local antibiotic therapy invarious infections.

Preferably, the antimicrobial coating further comprises additionalantimicrobial agents, such as silver or organic compounds, for example,sesquiterpenoids, penicillin, 2-benzimidazole carbamoyl. Preferably,silver in the form of nanoparticles are incorporated into theantimicrobial coating. More preferably, the silver nanoparticles are inthe size range of 1-100 nm. Methods of incorporating additionalantimicrobial agents into the substrate are known in the art. Forexample, silver may be incorporated into the coating by radical-mediateddispersion polymerization using radical initiators, such as AIBN, asdisclosed in Song et al., 2012. Other methods of incorporating theorganic antimicrobial agents into the substrate are reviewed in Kenawyet al., 2007.

An additional embodiment of the present invention is an ion-transportmembrane comprising any substrate disclosed herein. Such a membranewould allow for the diffusion of ions and are useful in, e.g., dialysis,desalination, gas separations, batteries and fuel cells. Exemplary iontransport membrane assemblies for fuel cells or batteries include thosedisclosed in, e.g., U.S. Pat. Nos. 6,565,632 and 7,335,247; and U.S.Patent Publication Nos. 2007/0137478, 2011/0294653, and 2011/0067405.Generally, fuel cells or batteries contain oxygen ion transportmembranes, which conduct oxygen ions. Oxygen ion transport membraneshave a cathode side, on which oxygen ionizes by gaining electrons. Thesubstrates disclosed herein are useful in coating the anode side of themembrane, on which the oxygen ions lose electrons and reconstitute intoelemental oxygen. Composite oxygen ion transport membranes are known inthe art and are disclosed in e.g., U.S. Pat. Nos. 7,556,676, 7,338,624,and 5,240,480; and U.S. Patent Publication Nos. 2005/0061663, and2005/0013933. The substrates disclosed herein are useful for(electro)dialysis because the electrical potential difference on the twosides of the membrane allows the transport of charged species.Electrodialysis apparatus are known in the art and are disclosed ine.g., U.S. Pat. Nos. 2,970,098, 5,643,430, 6,402,917, and 6,461,491; andU.S. Patent Publication No. 2005/0183956. One of the ways to desalinatewater is use an electrodialysis process in which pairs of anionic andcationic membranes are placed such that salt water is separated intodiluted solution and concentrated brine. Desalination systems are knownin the art and are disclosed in e.g., U.S. Pat. Nos. 4,539,088 and4,539,091; and U.S. Patent Publication No. 2011/0056876, 2010/0282689,and 2010/0314313.

Another embodiment of the present invention is a cell support comprisingany substrate disclosed herein. Such a cell support may be used forculturing of cells, such as e.g., stem cells. Generally, cell culturesare maintained in plastic dishes, the surface of which are negativelycharged. Thus, some anchorage-dependent cell types, such as stem cells,do not produce sufficient amounts of positively charged extracellularmatrix proteins, adhering only weakly to the plastic substratum.Accordingly, cationic substrates according to the present invention maybe used to provide support for such cells. Typically, the cationicsubstrates include a cyclopropenium ion according to the presentinvention as part of a polymeric system that also includes one or morecell culture compatible monomers such as, e.g., iminoethylene,methacrylate (e.g., choline methacrylate), and others known in the artsuch as those disclosed in Vendra et al., 2010.

Yet another embodiment of the present invention is a drug deliveryvehicle comprising a stable cationic dendritic polymer made according toany method disclosed herein. The cationic dendrite polymer of thepresent invention is well-suited to carry negatively charged DNA intoliving cells.

Drug delivery vehicles containing guanidine have also been shown to beeffective mimics of cell-penetrating peptides. The charged nature of acationic dendritic polymer made according to the methods disclosedherein can also be used to mimic these types of materials, which may beuseful in drug delivery. The high degree of branching of dendrimers alsomake them well-suited for drug delivery. For a review, see Gillies etal., 2005. Preferably, the core branches of the dendrimer are selectedso that they are compatible with introduction into living organisms,e.g., they are non-toxic and on-immunogenic. See, e.g., Vendra et al.,2010. The drug delivery vehicles of the present invention may be used todeliver one or more agents into a living organism, such as, e.g., a cellor a mammal, including a human. Representative, non-limiting examples ofdrugs that may be delivered according to the present invention includeadenosine deaminase, doxorubicin, interferon α-2b, and granulocytecolony stimulating factor.

A further embodiment of the present invention is a gene therapeuticvector comprising a stable cationic dendritic polymer made according toany method disclosed herein. Exemplary, non-limiting examples of monomerunits that may be incorporated into the dendritic polymer of the presentinvention include (poly)(β-aminoesters),(poly)(2-aminoethylpropylenephosphate), allylamine, and the like. See,e.g., Vendra et al., 2010.

As used herein, a “gene therapeutic vector” means a vehicle used totransfer genetic material to a target cell. The gene therapeutic vectormay be administered in vivo or in vitro. Preferably the cell is amammalian cell, but other types of cells, e.g., insect, plant, orfungal, or non-mammalian vertebrate cells may be used.

In operation, the genetic material, which may be nucleic acids, such asDNA, RNA, RNAi, mRNA, tRNA, short hairpin RNA (shRNA), short interferingRNA (siRNA), double-stranded RNA (dsRNA), transcriptional gene silencingRNA (ptgsRNA), Piwi-interacting RNA, pri-miRNA, pre-miRNA, micro-RNA(miRNA), or anti-miRNA (as described, e.g., in U.S. patent applicationSer. Nos. 11/429,720, 11/384,049, 11/418,870, and 11/429,720 andPublished International Application Nos. WO 2005/116250 and WO2006/126040), is reversibly linked to one or more of the dendritic corebranches. Upon delivery of the gene therapeutic vector to the targetcell, the nucleic acid(s) are released.

Additional Definitions

In the foregoing embodiments, the following definitions apply.

The term “alkoxy” refers to an alkyl group, preferably a lower alkylgroup, having an oxygen attached thereto. Representative alkoxy groupsinclude methoxy, ethoxy, propoxy, isopropoxy, tert-butoxy and the like.Other alkoxy groups within the scope of the present invention include,for example, the following:

The term “alkoxycarbonyl” refers to a carbonyl group substituted with analkoxy group.

The term “alkenyl”, as used herein, refers to an aliphatic groupcontaining at least one double bond and is intended to include both“unsubstituted alkenyls” and “substituted alkenyls”, the latter of whichrefers to alkenyl moieties having substituents replacing a hydrogen onone or more carbons of the alkenyl group. Such substituents may occur onone or more carbons that are included or not included in one or moredouble bonds. Moreover, such substituents include all those contemplatedfor alkyl groups, as discussed below, except where stability isprohibitive. For example, substitution of alkenyl groups by one or morealkyl, carbocyclyl, aryl, heterocyclyl, or heteroaryl groups iscontemplated.

The term “alkene functionalized” compound means a compound containing a—C═C group.

The term “alkenyloxy” refers to an alkenyl group having an oxygenattached thereto.

The term “alkenylthio”, as used herein, refers to a thiol groupsubstituted with an alkenyl group and may be represented by the generalformula alkenyl-S—.

The term “alkyl” refers to the radical of saturated aliphatic groups,including straight-chain alkyl groups, branched-chain alkyl groups,cycloalkyl (alicyclic) groups, alkyl-substituted cycloalkyl groups, andcycloalkyl-substituted alkyl groups. In certain embodiments, a straightchain or branched chain alkyl has 10 or fewer carbon atoms in itsbackbone (e.g., C₁-C₁₀ for straight chains, C₃-C₁₀ for branched chains).Likewise, certain cycloalkyls have from 3-8 carbon atoms in their ringstructure, including 5, 6 or 7 carbons in the ring structure.

Moreover, unless otherwise indicated, the term “alkyl” (or “loweralkyl”) as used throughout the specification, examples, and claims isintended to include both “unsubstituted alkyls” and “substitutedalkyls”, the latter of which refers to alkyl moieties havingsubstituents replacing a hydrogen on one or more carbons of thehydrocarbon backbone. Such substituents can include, for example, ahalogen, a hydroxyl, a carbonyl (such as a carboxyl, an alkoxycarbonyl,a formyl, or an acyl), a thiocarbonyl (such as a thioester, athioacetate, or a thioformate), an alkoxyl, a phosphoryl, a phosphate, aphosphonate, a phosphinate, an amino, an amido, an amidine, an imine, acyano, a nitro, an azido, a sulfhydryl, an alkylthio, a sulfate, asulfonate, a sulfamoyl, a sulfonamido, a sulfonyl, a heterocyclyl, anaralkyl, an aromatic, or heteroaromatic moiety. It will be understood bythose skilled in the art that the moieties substituted on thehydrocarbon chain can themselves be substituted, if appropriate. Forinstance, the substituents of a substituted alkyl may includesubstituted and unsubstituted forms of amino, azido, imino, amido,phosphoryl (including phosphonate and phosphinate), sulfonyl (includingsulfate, sulfonamido, sulfamoyl and sulfonate), and silyl groups, aswell as ethers, alkylthios, carbonyls (including ketones, aldehydes,carboxylates, and esters), —CF₃, —CN and the like. Exemplary substitutedalkyls are described below. Cycloalkyls can be further substituted withalkyls, alkenyls, alkoxys, alkylthios, aminoalkyls, carbonyl-substitutedalkyls, —CF3, —CN, and the like.

The term “Cx-y” when used in conjunction with a chemical moiety, suchas, alkyl, alkenyl, or alkoxy is meant to include groups that containfrom x to y carbons in the chain. For example, the term “C_(x-y)alkyl”refers to substituted or unsubstituted saturated hydrocarbon groups,including straight-chain alkyl and branched-chain alkyl groups thatcontain from x to y carbons in the chain, including haloalkyl groupssuch as trifluoromethyl and 2,2,2-trifluoroethyl, etc. The terms“C_(2-y)alkenyl” and “C_(2-y)alkynyl” refer to substituted orunsubstituted unsaturated aliphatic groups analogous in length andpossible substitution to the alkyls described above, but that contain atleast one double or triple bond respectively.

The term “alkylamino”, as used herein, refers to an amino groupsubstituted with at least one alkyl group.

The term “alkylsulfinyl” means a sulfinyl group substituted with analkyl group.

The term “alkylsulfonyl” means a sulfonyl group substituted with analkyl group.

The term “alkylthio”, as used herein, refers to a thiol groupsubstituted with an alkyl group and may be represented by the generalformula alkylS—.

The term “alkynyl”, as used herein, refers to an aliphatic groupcontaining at least one triple bond and is intended to include both“unsubstituted alkynyls” and “substituted alkynyls”, the latter of whichrefers to alkynyl moieties having substituents replacing a hydrogen onone or more carbons of the alkynyl group. Such substituents may occur onone or more carbons that are included or not included in one or moretriple bonds. Moreover, such substituents include all those contemplatedfor alkyl groups, as discussed above, except where stability isprohibitive. For example, substitution of alkynyl groups by one or morealkyl, carbocyclyl, aryl, heterocyclyl, or heteroaryl groups iscontemplated.

The term “alkynyloxy” means an alkynyl group having an oxygen attachedthereto.

The term “alkynylthio”, as used herein, refers to a thiol groupsubstituted with an alkynyl group and may be represented by the generalformula alknyl-S—.

The term “amide”, as used herein in the context of polymers, refers to abackbone containing the functional group:

wherein R⁷ represent a hydrogen or hydrocarbyl group.

The term “amido”, as used herein, refers to a group

wherein R⁷ and R⁸ each independently represent a hydrogen or hydrocarbylgroup, or R⁷ and R⁸ taken together with the N atom to which they areattached complete a heterocycle having from 4 to 8 atoms in the ringstructure.

The terms “amine” and “amino” are art-recognized and refer to bothunsubstituted and substituted amines and salts thereof, e.g., a moietythat can be represented by

wherein R⁷, R⁸, and R^(8′) each independently represent a hydrogen or ahydrocarbyl group, or R⁷ and R⁸ taken together with the N atom to whichthey are attached complete a heterocycle having from 4 to 8 atoms in thering structure. The term “primary” amine means only one of R⁷ and R⁸ orone of R⁷, R⁸, and R^(8′) is a hydrocarbyl group. Secondary amines havetwo hydrocarbyl groups bound to N. In tertiary amines, all three groups,R⁷, R⁸, and R^(8′), are replaced by hydrocarbyl groups.

The term “aryl” as used herein includes substituted or unsubstitutedsingle-ring aromatic groups in which each atom of the ring is carbon.Preferably the ring is a 3- to 8-membered ring, more preferably a6-membered ring. The term “aryl” also includes polycyclic ring systemshaving two or more cyclic rings in which two or more carbons are commonto two adjoining rings wherein at least one of the rings is aromatic,e.g., the other cyclic rings can be cycloalkyls, cycloalkenyls,cycloalkynyls, aryls, heteroaryls, and/or heterocyclyls. Aryl groupsinclude benzene, naphthalene, phenanthrene, phenol, aniline, and thelike.

As used herein, “aryloxy” means which an aryl group singularly bonded tooxygen.

The term “aryl-alkyl” means an alkyl group substituted with aryl.

The term “aryl-heteroalkyl” means an heteroalkyl group substituted witharyl.

The term “azide” means a functional group containing —N₃.

The terms “carbocycle”, “carbocyclyl”, and “carbocyclic”, as usedherein, refer to a non-aromatic saturated or unsaturated ring in whicheach atom of the ring is carbon. Preferably a carbocycle ring containsfrom 3 to 8 atoms, including 5 to 7 atoms, such as for example, 6 atoms.

The term “carbonyl” means a functional group composed of a carbon atomdouble-bonded to an oxygen atom: C═O. Carbonyls include withoutlimitation, aldehydes, ketones, carboxylic acids, esters, and amides.

The terms “carboxy” and “carboxyl”, as used herein, refer to a grouprepresented by the formula —CO₂H.

The term “carboxylate” refers to the conjugate base of a carboxyl group,represented by the formula —COO⁻.

The term “cyano” means of a functional group composed of a carbon atomtriple-bonded to a nitrogen atom: —C≡N.

The term “cycloalkyl” means a univalent groups derived from cycloalkanesby removal of a hydrogen atom from a ring carbon atom.

The term “cycloalkenyl” means a univalent groups derived fromcycloalkenes by removal of a hydrogen atom from a ring carbon atom.

The term “ester”, as used herein in the context of polymers, refers to abackbone containing the functional group:

The term “ether”, as used herein, refers to a hydrocarbyl group linkedthrough an oxygen to another hydrocarbyl group. Accordingly, an ethersubstituent of a hydrocarbyl group may be hydrocarbyl-O—. Ethers may beeither symmetrical or unsymmetrical. Examples of ethers include, but arenot limited to, heterocycle-O-heterocycle and aryl-O-heterocycle. Ethersinclude “alkoxyalkyl” groups, which may be represented by the generalformula alkyl-O-alkyl.

The term “ethylene” as used herein in the context of polymers, refers toa backbone containing the functional group:

The term “ethylene terephthalate refers to the following functionalgroup:

The terms “halo” and “halogen” are used interchangeably herein and meanhalogen and include chloro, fluoro, bromo, and iodo.

The term “heteroaryl” includes substituted or unsubstituted aromaticsingle ring structures, preferably 3- to 8-membered rings, morepreferably 5- to 7-membered rings, even more preferably 5- to 6-memberedrings, whose ring structures include at least one heteroatom, preferablyone to four heteroatoms, more preferably one or two heteroatoms. Theterm “heteroaryl” also includes polycyclic ring systems having two ormore cyclic rings in which two or more carbons are common to twoadjoining rings wherein at least one of the rings is heteroaromatic,e.g., the other cyclic rings can be cycloalkyls, cycloalkenyls,cycloalkynyls, aryls, heteroaryls, and/or heterocyclyls. Heteroarylgroups include, for example, pyrrole, furan, thiophene, imidazole,oxazole, thiazole, pyrazole, pyridine, pyrazine, pyridazine, andpyrimidine, and the like.

As used herein, “heteroaryloxy” means which a heteroaryl groupsingularly bonded to oxygen.

“Heteroaryl-alkyl” means a alkyl group substituted with a heteroarylgroup.

“Heteroaryl-heteroalkyl” means a heteroalkyl group substituted with aheteroaryl group.

The term “heteroatom” as used herein means an atom of any element otherthan carbon or hydrogen. Preferred heteroatoms are nitrogen, oxygen, andsulfur.

The term “heteroalkyl” means an alkyl in which at least one carbon of ahydrocarbon backbone is substituted with a heteroatom. Heteroalkylsinclude alkoxyalkyls, such as C₁₋₈ alkoxyalkyl.

The term “heteroaromatic” means at least one carbon atoms in thearomatic group is substituted with a heteroatom.

The terms “heterocyclyl”, “heterocycle”, “heterocyclic”, and the likerefer to substituted or unsubstituted non-aromatic ring structures,preferably 3- to 8-membered rings, whose ring structures include atleast one heteroatom, preferably one to four heteroatoms, morepreferably one or two heteroatoms. For example, “nitrogen heterocycle”means to substituted or unsubstituted non-aromatic ring structures,whose ring structures contain at least one nitrogen. The terms“heterocyclyl,” “heterocyclic,” and the like also include polycyclicring systems having two or more cyclic rings in which two or morecarbons are common to two adjoining rings wherein at least one of therings is heterocyclic, e.g., the other cyclic rings can be cycloalkyls,cycloalkenyls, cycloalkynyls, aryls, heteroaryls, and/or heterocyclyls.Heterocyclyl groups include, for example, piperidine, piperazine,pyrrolidine, morpholine, lactones, lactams, and the like.

The term “hydrocarbyl”, as used herein, refers to a group that is bondedthrough a carbon atom that does not have a ═O or ═S substituent, andtypically has at least one carbon-hydrogen bond and a primarily carbonbackbone, but may optionally include heteroatoms. Thus, groups likemethyl, ethoxyethyl, 2-pyridyl, and trifluoromethyl are considered to behydrocarbyl for the purposes of this application, but substituents suchas acetyl (which has a ═O substituent on the linking carbon) and ethoxy(which is linked through oxygen, not carbon) are not. Hydrocarbyl groupsinclude, but are not limited to aryl, heteroaryl, carbocycle,heterocycle, alkyl, alkenyl, alkynyl, and combinations thereof.

The term “hydroxyalkyl”, as used herein, refers to an alkyl groupsubstituted with a hydroxy group.

The term “hydroxyl” or “hydroxy,” as used herein, refers to the group—OH.

The term “imino” group means a functional group containing acarbon-nitrogen double bond.

The term “lower” when used in conjunction with a chemical moiety, suchas, acyl, alkyl, alkenyl, alkynyl, or alkoxy is meant to include groupswhere there are ten or fewer non-hydrogen atoms in the substituent,preferably eight or fewer, such as for example, from about 2 to 8 carbonatoms, including less than 6 carbon atoms. A “lower alkyl”, for example,refers to an alkyl group that contains ten or fewer carbon atoms,preferably eight or fewer. In certain embodiments, acyl, alkyl, alkenyl,alkynyl, or alkoxy substituents defined herein are respectively loweracyl, lower alkyl, lower alkenyl, lower alkynyl, or lower alkoxy,whether they appear alone or in combination with other substituents,such as in the recitations hydroxyalkyl and aralkyl (in which case, forexample, the atoms within the aryl group are not counted when countingthe carbon atoms in the alkyl substituent).

The term “(meth)acrylate” refers to the following functional group:

The term “nitro” means the functional group —NO₂.

The term “norbornene” refers to the following functional group:

The terms “polycyclyl”, “polycycle”, and “polycyclic” refer to two ormore rings (e.g., cycloalkyls, cycloalkenyls, cycloalkynyls, aryls,heteroaryls, and/or heterocyclyls) in which two or more atoms are commonto two adjoining rings, e.g., the rings are “fused rings”. Each of therings of the polycycle can be substituted or unsubstituted. In certainembodiments, each ring of the polycycle contains from 3 to 10 atoms inthe ring, preferably from 3 to 8, such as for example, 5 to 7.

The term “propylene” refers to the following functional group:

The term “oxo” refers to the group ═O.

The term “substituted” refers to moieties having substituents replacinga hydrogen on one or more carbons of the backbone. It will be understoodthat “substitution” or “substituted with” includes the implicit provisothat such substitution is in accordance with the permitted valence ofthe substituted atom and the substituent, and that the substitutionresults in a stable compound, e.g., which does not spontaneously undergotransformation such as by rearrangement, cyclization, elimination, etc.As used herein, the term “substituted” is contemplated to include allpermissible substituents of organic compounds. In a broad aspect, thepermissible substituents include acyclic and cyclic, branched andunbranched, carbocyclic and heterocyclic, aromatic and non-aromaticsubstituents of organic compounds. The permissible substituents can beone or more and the same or different for appropriate organic compounds.For purposes of this invention, the heteroatoms such as nitrogen mayhave hydrogen substituents and/or any permissible substituents oforganic compounds described herein which satisfy the valences of theheteroatoms. Substituents can include any substituents described herein,for example, a halogen, a hydroxyl, a carbonyl (such as a carboxyl, analkoxycarbonyl, a formyl, or an acyl), a thiocarbonyl (such as athioester, a thioacetate, or a thioformate), an alkoxyl, a phosphoryl, aphosphate, a phosphonate, a phosphinate, an amino, an amido, an amidine,an imine, a cyano, a nitro, an azido, a sulfhydryl, an alkylthio, asulfate, a sulfonate, a sulfamoyl, a sulfonamido, a sulfonyl, aheterocyclyl, an aralkyl, or an aromatic or heteroaromatic moiety. Itwill be understood by those skilled in the art that the moietiessubstituted on the hydrocarbon chain can themselves be substituted, ifappropriate.

The term “styrene” refers to the following functional group:

As used herein, the term “substituent,” means H, cyano, oxo, nitro,acyl, acylamino, halogen, hydroxy, amino acid, amine, amide, carbamate,ester, ether, carboxylic acid, thio, thioalkyl, thioester, thioether,C₁₋₈ alkyl, C₁₋₈alkoxy, C₁₋₈alkenyl, C₁₋₈aralkyl, 3- to 8-memberedcarbocyclic, 3- to 8-membered heterocyclic, 3- to 8-membered aryl, or 3-to 8-membered heteroaryl, sulfate, sulfonamide, sulfoxide, sulfonate,sulfone, alkylsulfonyl, and arylsulfonyl.

Unless specifically stated as “unsubstituted,” references to chemicalmoieties herein are understood to include substituted variants. Forexample, reference to an “aryl” group or moiety implicitly includes bothsubstituted and unsubstituted variants.

The term “sulfate” is art-recognized and refers to the group —OSO₃H, ora pharmaceutically acceptable salt thereof.

The term “sulfinyl” is art-recognized and refers to the group —S(O)—R⁷wherein R⁷ represents a hydrocarbyl.

The term “sulfonyl” is refers to the group —S(O)₂—R⁷, wherein R⁷represents a hydrocarbyl.

The term “thio” or “thiol”, as used herein, refers to the —SH group.

The term “thioalkyl”, as used herein, refers to an alkyl groupsubstituted with a thiol group.

The term “thiono” refers to a substitution on a carbon atom, morespecifically to a doubly bonded sulfur.

The term “urethane” refers to the following functional group:

wherein R and R′ are independently selected from aryls or alkyls.

The term “vinyl chloride” refers to the following functional group:

It is understood that the disclosure of a compound herein encompassesall stereoisomers of that compound. As used herein, the term“stereoisomer” refers to a compound made up of the same atoms bonded bythe same bonds but having different three-dimensional structures whichare not interchangeable. The three-dimensional structures are calledconfigurations. Stereoisomers include enantiomers, optical isomers, anddiastereomers.

The terms “racemate” or “racemic mixture” refer to a mixture of equalparts of enantiomers. The term “chiral center” refers to a carbon atomto which four different groups are attached. The term “enantiomericenrichment” as used herein refers to the increase in the amount of oneenantiomer as compared to the other.

It is appreciated that compounds of the present invention having achiral center may exist in and be isolated in optically active andracemic forms. Some compounds may exhibit polymorphism. It is to beunderstood that the present invention encompasses any racemic,optically-active, diastereomeric, polymorphic, or stereoisomeric form,or mixtures thereof, of a compound of the invention, which possess theuseful properties described herein, it being well known in the art howto prepare optically active forms (for example, by resolution of theracemic form by recrystallization techniques, by synthesis fromoptically-active starting materials, by chiral synthesis, or bychromatographic separation using a chiral stationary phase).

Examples of methods to obtain optically active materials are known inthe art, and include at least the following:

-   -   i) physical separation of crystals—a technique whereby        macroscopic crystals of the individual enantiomers are manually        separated. This technique can be used if crystals of the        separate enantiomers exist, i.e., the material is a        conglomerate, and the crystals are visually distinct;    -   ii) simultaneous crystallization—a technique whereby the        individual enantiomers are separately crystallized from a        solution of the racemate, possible only if the latter is a        conglomerate in the solid state;    -   iii) enzymatic resolutions—a technique whereby partial or        complete separation of a racemate by virtue of differing rates        of reaction for the enantiomers with an enzyme;    -   iv) enzymatic asymmetric synthesis—a synthetic technique whereby        at least one step of the synthesis uses an enzymatic reaction to        obtain an enantiomerically pure or enriched synthetic precursor        of the desired enantiomer;    -   v) chemical asymmetric synthesis—a synthetic technique whereby        the desired enantiomer is synthesized from an achiral precursor        under conditions that produce asymmetry (i.e., chirality) in the        product, which may be achieved using chiral catalysts as        disclosed in more detail herein or chiral auxiliaries;    -   vi) diastereomer separations—a technique whereby a racemic        compound is reacted with an enantiomerically pure reagent (the        chiral auxiliary) that converts the individual enantiomers to        diastereomers. The resulting diastereomers are then separated by        chromatography or crystallization by virtue of their now more        distinct structural differences and the chiral auxiliary later        removed to obtain the desired enantiomer;    -   vii) first- and second-order asymmetric transformations—a        technique whereby diastereomers from the racemate equilibrate to        yield a preponderance in solution of the diastereomer from the        desired enantiomer or where preferential crystallization of the        diastereomer from the desired enantiomer perturbs the        equilibrium such that eventually in principle all the material        is converted to the crystalline diastereomer from the desired        enantiomer. The desired enantiomer is then released from the        diastereomer;    -   viii) kinetic resolutions—this technique refers to the        achievement of partial or complete resolution of a racemate (or        of a further resolution of a partially resolved compound) by        virtue of unequal reaction rates of the enantiomers with a        chiral, non-racemic reagent or catalyst under kinetic        conditions;    -   ix) enantiospecific synthesis from non-racemic precursors—a        synthetic technique whereby the desired enantiomer is obtained        from non-chiral starting materials and where the stereochemical        integrity is not or is only minimally compromised over the        course of the synthesis;    -   x) chiral liquid chromatography—a technique whereby the        enantiomers of a racemate are separated in a liquid mobile phase        by virtue of their differing interactions with a stationary        phase. The stationary phase can be made of chiral material or        the mobile phase can contain an additional chiral material to        provoke the differing interactions;    -   xi) chiral gas chromatography—a technique whereby the racemate        is volatilized and enantiomers are separated by virtue of their        differing interactions in the gaseous mobile phase with a column        containing a fixed non-racemic chiral adsorbent phase;    -   xii) extraction with chiral solvents—a technique whereby the        enantiomers are separated by virtue of preferential dissolution        of one enantiomer into a particular chiral solvent;    -   xiii) transport across chiral membranes—a technique whereby a        racemate is placed in contact with a thin membrane barrier. The        barrier typically separates two miscible fluids, one containing        the racemate, and a driving force such as concentration or        pressure differential causes preferential transport across the        membrane barrier. Separation occurs as a result of the        non-racemic chiral nature of the membrane which allows only one        enantiomer of the racemate to pass through.

The stereoisomers may also be separated by usual techniques known tothose skilled in the art including fractional crystallization of thebases or their salts or chromatographic techniques such as LC or flashchromatography. The (+) enantiomer can be separated from the (−)enantiomer using techniques and procedures well known in the art, suchas that described by J. Jacques, et al., antiomers, Racemates, andResolutions”, John Wiley and Sons, Inc., 1981. For example, chiralchromatography with a suitable organic solvent, such asethanol/acetonitrile and Chiralpak AD packing, 20 micron can also beutilized to effect separation of the enantiomers.

The following examples are provided to further illustrate the compounds,compositions, and processes of the present invention. These examples areillustrative only and are not intended to limit the scope of theinvention in any way.

EXAMPLES Example 1 Synthesis of Cyclopropenium Ions

Diaminochlorocyclopropenium Ions (Formula 4)

A diaminochlorocyclopropenium ion (a compound within the scope ofFormula 4, where R₁ and R₂ are H) may be synthesized according toequation (1) or equation (2), depending on the size of the R₁R₂ groupsbeing added to tetrachlorocyclopropene (Compound 1). Bulkier groups(such as branched groups) tend to add twice, as in equation 1, whereassmaller groups (such as linear or straight chain groups) tend to addthree times, as in equation 2. See also Yoshida, 1973. In the Examples,unless specifically defined otherwise, the R groups are as definedpreviously in this application.

In general, an excess secondary amine of the formula HNR₁R₂(Formula 2)is added to tetrachlorocyclopropene (compound 1) in methylene chloride.Formula 3 or Formula 4 is obtained after removal of the solvent. Ingeneral, removal of solvent is all that is required. If desired, columnchromatography may be used after any step. The identity and purity ofthe compound may be confirmed by H-NMR, C-NMR and low-resolution massspectrometry.

If the reaction proceeds according to equation (2), water solubleFormula 3 may be converted to Formula 4 by the addition of potassiumhydroxide in water followed by reaction with oxalyl chloride. If Formula3 is not soluble in water, then a water/methanol mixture is used, andthe reaction mixture is heated to 60° C.-80° C. to solubilize Formula 3.The reaction with oxalyl chloride is done in dichloromethane solvent atroom temperature.

Formula 4 in which R₁═R₂=Cyclohexyl.

A compound within the scope of Formula 4 in which R₁═R₂=cyclohexyl wassynthesized as follows. To a solution of tetrachlorocyclopropene 1, anexcess amount of dicyclohexylamine (Sigma Aldrich, St. Louis, Mo.) wasadded. The reaction mixture was stirred overnight at room temperature,followed by filtration and a 1 M HCl washing.

Formula 4 in which R₁═R₂=Isopropyl

A compound within the scope of Formula 4 in which R₁═R₂=isopropyl wasmade similarly to the cyclohexyl variant, with the exception that thework-up consists of only removal of the solvent. This process yieldsFormula 4 (where R₁═R₂=isopropyl) and a diisopropylamine hydrochloridesalt in a 1:1 mixture. The diisopropylamine was purchased from SigmaAldrich.

Formula 3 in which R₁═R₂=Methyl or R₁═R₂═—(CH₂)₄—

A compound within the scope of Formula 3 where R₁═R₂=Me orR₁═R₂═—(CH₂)₄— were prepared following Breslow's protocol (Wilcox andBreslow, 1980). Conversion (step 2) was performed in dichloromethane byaddition of oxalyl chloride to cyclopropenone intermediate. Unlessotherwise noted, all starting materials in the Examples were purchasedfrom Sigma Aldrich.

Cyclopropenium Ions (Formula 6)

A diaminochlorocyclopropenium ion (a compound within the scope ofFormula 4) is reacted with an excess of a secondary amine of the formulaHNR₃R₄ (Formula 5) in methylene chloride. A compound within the scope ofFormula 6 is obtained after removal of the solvent. If necessary, awater or 1 M HCl washing may be used to remove excess amine beforeremoval of solvent.

Example 2 Synthesis of Cross-Linked Polymer 22

Synthesis of Compound 21

Tetrachlorocyclopropene (Compound 1) was reacted with excessdiallylamine (Sigma Aldrich, catalog No. D9603, St. Louis, Mo.) inmethylene chloride. After a water/1 M HCl washing and the removal ofsolvent, the cyclopropenium compound 21 was obtained.

Cross-linked Polymer 22 was generated using the thiol-ene chemistrydescribed in Campos et al., 2008a.

In particular, poly[(mercaptopropyl)methylsiloxane] (PMMS) (molecularweight of approximately 4000-7000 g/mol) (which is within the scope ofpolymer 20) was reacted with cyclopropenium ion 21 in the presence ofless than 0.1 wt % 2,2-dimethoxy-2-phenylacetophenone (DMPA) as theinitiator. Curing with ultraviolet (UV) light resulted in thecross-linked polymer 22. Different ratios of PMMS to cyclopropenium ion21 may be used. Ratios of 1:1, 1:2, and 2:1 by mass were used. Theresultant polymers are stiffer when a higher mass percentage ofcyclopropenium ion 21 was used. All of the polymers, however, areflexible enough to be distorted by hand. An image of the cross-linkedpolymer is shown in FIG. 3.

Thermally Initiated Reactions

Alternatively, the reaction is initiated thermally, using any thermalradical initiator to form polymer 22. For example,azobisisobutyronitrile (AIBN) is a radical initiator that can be blendedin the system (for example, 3-10 wt %) and the polymerization can takeplace at temperatures higher than 70° C. If a different initiator isused with either a higher or lower decomposition temperature, then thecross-linking temperature can be varied as desired. Cross-linking timecan also be varied from 5 minutes to several hours, depending on thetemperature and radical initiator of choice.

Example 3 Synthesis of Other Cross-Linked Polymers

Many other cross-linked polymers may be obtained by reacting, e.g., anyof the thiol compounds with any of the ene compounds listed below. Theinitiator for the reaction(s) may be, e.g., either AIBN as the thermoinitiator or DMPA.

Synthesis of Compound 25

Tetrachlorocyclopropene (Compound 1) was reacted with excessN-allylmethylamine (Sigma Aldrich, catalog No. 317748) in methylenechloride. After a water/1M HCl wash and the removal of solvent,cyclopropenium compound 25 was obtained.

Synthesis of Compound 23

The double bonds in compound 21 are reacted with thioacetic acid to formthe corresponding thioester, which is then hydrolyzed under aceticconditions to form compound 23.

Synthesis of Compound 24

The double bonds in compound 25 are reacted with thioacetic acid to formthe corresponding thioester, which is then hydrolyzed under aceticconditions to form compound 24.

Example 4 Synthesis of Linear Polymer Using “Grafting Though” Method

Linear polymers are made by the grafting through method using functionalgroups on the cyclopropenium group to form the polymer backbones (e.g.,polymers based on styrene, (meth)acrylates, norbonenes). Randomcopolymers and block copolymers are also made.

Polymers with Polystyrene Backbones, Polymer 33

R₁, R₂:

A compound within the scope of Formula 4 is reacted with excess1-piperazineethanol (compound 30) (Sigma Aldrich catalog number H28807)in methylene chloride to form compound 31. In this example, R₁ and R₂may be the same or different and are independently selected from, e.g.,the groups listed above.

A compound within the scope of Formula 32 is made by treatment of acompound within the scope of Formula 31 with sodium hydride, followed byaddition of 4-vinylbenzylchloride in DMF or THF. The resulting product,a compound within the scope of Formula 32, is purified by columnchromatography.

A polymer within the scope of Formula 33 may be formed in accordancewith Campos et al., 2008b. Briefly, a catalytic amount of AIBN is addedto a compound within the scope of Formula 32 with a reversibleaddition-fragmentation chain transfer (RAFT) agent,

and heated. The contents are diluted with CH₂Cl₂ before precipitatinginto cold MeOH. The resulting polymer is dried in vacuo.Polymers with Polystyrene Backbones, Formula 37

R₁, R₂:

A compound within the scope of Formula 4 is reacted with excess2-(Methylamino)ethanol (compound 34) (Sigma Aldrich catalog number471445) in methylene chloride to form a compound within the scope ofFormula 35. In this example, R₁ and R₂ may be the same or different andare independently selected from, e.g., the groups listed above.

A compound within the scope of Formula 36 is made by treating a compoundwithin the scope of Formula 35 with sodium hydride, followed by additionof 4-vinylbenzylchloride in DMF or THF. The resulting product, which iswithin the scope of Formula 36, is purified by column chromatography.

A polymer within the scope of Formula 37 may be formed in accordancewith Campos et al., 2008b. Briefly, a catalytic amount of AIBN is addedto a compound within the scope of Formula 36 in combination with areversible addition-fragmentation chain transfer (RAFT) agent,

and heated. The contents are diluted with CH₂Cl₂ before precipitatinginto cold MeOH. The resulting polymer, which is within the scope ofFormula 37, is dried in vacuo. Depending on the solubility, the polymermay be precipitated into hexanes or a water/MeOH mixture. Precipitationtests can be performed on a small scale before scaling up.Polymers with Polymethacrylate Backbones, Formula 39

A compound within the scope of Formula 31 is dissolved indichloromethane, cooled to 00° C., then triethylamine and methacryloylchloride are added in excess. The reaction is then allowed to proceedovernight; followed by a water washing and column chromatography. Theresulting product is a compound within the scope of Formula 38.

A polymer within the scope of Formula 39 may be formed in accordancewith Campos et al., 2008b. Briefly, a compound within the scope ofFormula 38, ethyl-2-bromo isobutyrate, andN,N,N′,N″,N″-pentamethyldiethylenetriamine (PMDETA) are added to a flaskand sparged with nitrogen. Copper(I) bromide is placed in a Schlenkflask with a stir bar and evacuated. The reagent mixture is heated to75° C., with stirring. The solution is then diluted with CH₂Cl₂ andpassed through neutral alumina to remove the excess copper. The solutionis concentrated, and a polymer within the scope of Formula 39 isprecipitated into hexanes and dried under vacuo as a final step.Additionally, precipitation may take place into methanol instead ofhexanes, depending on the solubility of the polymer.

Polymers with Polymethacrylate Backbones, Formula 41

A compound within the scope of Formula 35 is dissolved indichloromethane, and the mixture is cooled to 0° C. Then triethylamineand methacryloyl chloride (Sigma Aldrich) are added in excess. Thereaction is then allowed to proceed overnight. A water washing andcolumn chromatography yield a compound within the scope of Formula 40.

A polymer within the scope of Formula 41 may be formed in accordancewith Campos et al., 2008b. Briefly, a compound within the scope ofFormula 40, ethyl-2-bromo isobutyrate, andN,N,N′,N″,N″-pentamethyldiethylenetriamine (PMDETA) are added to a flaskand sparged with nitrogen. Copper(I) bromide is placed in a Schlenkflask with a stir bar and evacuated. The reagent mixture is heated to75° C., with stirring. The solution is then diluted with CH₂Cl₂ andpassed through neutral alumina to remove the excess copper. The solutionis concentrated, and the a polymer within the scope of Formula 41 isprecipitated into hexanes.

Example 5 Synthesis of Linear Polymer Using “Grafting To” Method

The cyclopropenium group may also be grafted onto a pre-formed polymerusing, e.g., click chemistry reactions, such as thiol-ene andazide/alkyne click reactions, as illustrated in FIG. 1. Suitablecompounds for such click chemistry reactions include those shown below:

R₁, R₂:

For example, a compound within the scope of Formula 42 is used in areaction of a primary amine with an NHS-activated ester to make acorresponding amide. Compounds within the scope of Formulas 43 and 44are used, e.g., in azide/alkyne click reactions, and a compound withinthe scope of Formula 45 is used in thiol-ene reactions, in accordancewith the procedure disclosed in Campos et al., 2008b.

Each of the starting compounds within the scope of Formulas 42-45 ismade according to the synthesis scheme of equation 1 or 2, followed byequation 3.

As an alternative, a compound within the scope of Formula 45 may beformed according to the following synthesis scheme:

A compound within the scope of Formula 4 is reacted with excessN-allylmethylamine (Sigma Aldrich, catalog No. 317748) in methylenechloride. A cyclopropenium compound within the scope of Formula 46 isobtained after removal of solvent. The double bond in a compound withinthe scope of Formula 46 is reacted with thioacetic acid to form thecorresponding thioester, which is then hydrolyzed under acidicconditions to form a compound within the scope of Formula 45.

Example 6 Synthesis of Cyclopropenium Dendrimers

Dendrimers are synthesized using trifunctional monomers as shown in FIG.2. Many different strategies may be used to generate dentrimers with acore cyclopropenium cation.

For example, an accelerated AB₂/CD₂ approach using both copper catalyzedazide alkyne cycloaddition (CuAAC) and a thiol-ene coupling reaction maybe used to generate dendrimers, as disclosed in Antoni et al., 2010.Specifically, the following representative compounds are used for thestrategy.

Compounds 46 and 47 will be used in one dendrimer synthesis, andcompounds 46 and 48 will be used in another. The synthesis of compound47 is disclosed in Antoni et al., 2010.

Synthesis of Compound 46

Compound 25 is converted to compound 49 by the addition of potassiumhydroxide in water followed by reaction with oxalyl chloride. Compound49 is then reacted with excess methyl propargyl amine to yield compound46.

Synthesis of Compound 48

Tetrachlorocyclopropene (Compound 1) is reacted with excess2-(methylamino)ethanol (compound 34) (Sigma Aldrich catalog number471445) in accordance with equations 1 or 2 above to form compound 50.

Compound 50 is then reacted with excess N-allylmethylamine (SigmaAldrich, catalog No. 317748) in methylene chloride. The double bonds inthe resulting product are reacted with thioacetic acid to form thecorresponding thioester, which is then hydrolyzed under aceticconditions to form the thiol group in compound 48. Esterification withthe azide functional monomer yields compound 48.

First Generation Dendrimer: Thiol-Ene Reaction

A first generation dendrimer may be obtained via a thiol-ene reactionbetween compounds 46 and 47 or compounds 46 and 48. The reaction isconducted in the presence of tris(allyloxy)triazine (TAT), as well asthe radical initiator, 2,2-dimethoxy-2-phenylacetophenone (DMPA). Thereaction solution is sparged with argon prior to irradiation with 365 nmUV light followed by simple filtration through a plug of silica toremove excess compound 47 or 48.

Second Generation Dendrimer: CuAAC Reaction

Purified first generation dendrimer is then reacted with 1.1 equivalentsof 47 or 48 in THF/H₂O with CuSO₄ and sodium ascorbate (NaAsc). TheCuSO₄/NaAsc system (Rostovtsev et al., 2002) is chosen because of itsproven robust nature and monitoring of the CuAAC reaction using ¹H NMRand FT-IR spectroscopy revealed full conversion of the peripheralazides. Concomitant with the loss of the CH₂N₃ resonance at 3.3 ppm, newpeaks in the region of 5.1-5.9 ppm corresponding to the terminal alkenesof the fully converted second generation dendrimer may be observed inthe ¹H NMR spectrum. Additionally, FT-IR will be able to show completedisappearance of the azide stretch at 2091 cm⁻¹ and reappearance of theterminal alkene vibrational transition at 923 cm⁻¹, thus confirming thequantitative nature of the second generation growth step.

Higher Generation Dendrimers

Higher generation dendrimers may be formed by performing additionalcycles of the thiol/ene reaction (by utilizing, e.g., the process formaking of the first generation dendrimer) and the CuAAC reaction (byutilizing, e.g., the process for making of the second generationdendrimer). Optionally, additional purification steps, for example, byfiltration through a silica plug, simple precipitation, or a combinationof extraction and precipitation, may be performed.

Example 7 Alternative Methods of Synthesizing Cyclopropenium-ContainingPolymers

A further novel route according to the present invention to synthesizecyclopropenium containing polymers has been developed. In this method, arandom copolymer of styrene and chloromethylstyrene (or a homopolymer ofchloromethylstyrene) is reacted with either methylamine orisopropylamine to introduce an amine functional handle into the polymer.The resulting amine functionalized polymer is then reacted withdichlorocyclopropene in a substitution reaction to yield atris(dialkylamino)cyclopropenium containing polymer. The reaction schemefor converting polymers containing polychloromethylstyrene topoly(N-alkylamino)methylstyrene, followed by substitution of thedichlorocyclopropene is as follows:

In the scheme above, x and y are independently selected from integersgreater than or equal to zero, such as from 0-1,000, including 0-500,0-250, 0-100, 0-50, 0-25, 0-10, and 0-5.

Furthermore, this methodology may be applied to diblock copolymers tocreate cyclopropenium containing diblocks for the first time. Thefollowing scheme shows how diblock copolymers may be made using thismethod:

In the scheme above, x, y, and z are independently selected fromintegers greater than or equal to zero, such as from 0-1,000, including0-500, 0-250, 0-100, 0-50, 0-25, 0-10, and 0-5. For example, x, y, and zmay be independently selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10.R is any group that suitable for participating in the process, includingsubstituted or unsubstituted alkyl, such as C₁₋₆ alkyl, preferablymethyl or isopropyl groups.

Diblock copolymers can self-assemble into nanoscale patterns, and thus,nanopatterned cyclopropenium-containing surfaces may be made.

Example 8 Alternative Methods of Synthesizing Cyclopropenium Monomers

Exploration of the CP functional group in the context of cationicpolyelectrolytes was originally inspired by its ionic liquid properties(Curnow et al. 2011) and the straightforward elaboration of the CP ionwith various functional groups. Thus far, however, there are no reportson the incorporation of this thermodynamically stable carbocation intomacromolecules; CP derivatives have only appeared in polymers astransient species (Weidner et al. 1995, Peart et al. 2010 (Weidner etal. 1995, Peart et al. 2010). Derivatives of the CP ion are made frominexpensive reagents and can be easily prepared on a multi-gram scaleunder ambient conditions (Curnow et al. 2011). As robust chemistry isrequisite for large-scale production of materials, we devised a viablesynthetic strategy en route to the polymerisable CP ion monomers. Thegeneral approach to synthesize CP ion-containing monomers is based onthe facile preparation of asymmetric amino-substituted CP ions (forexample, CPR, FIG. 4) (Curnow et al. 2012). This procedure allows us tointimately change functionality while maintaining cationic propertiesand thermal stability. Notably, synthetic routes to aminocyclopropeniumderivatives are modular and highly scalable (Bandar et al. 2013a), withefficiency levels approaching those attained via click chemistry (Kolbet al. 2001).

Referring to FIG. 5, the preparation of the CPR monomers begins withpenta-chlorocyclopropane (1), which is commercially available orinexpensively synthesized in hundred-gram quantities (Tobey et al.1966). Reaction of 1 with a secondary amine leads to near-quantitativeyields of a corresponding CP cation (2 or 3). Thus, amines with highsteric hindrance (dicyclohexylamine, Cy and diisopropylamine, iP) addtwice to 1, preventing addition of a third bulky amine and leadingdirectly to 2. Conversely, less sterically hindered amines, such asmorpholine (Mo), add thrice to 1, resulting in a tris-amino CP (3). Thelatter is readily hydrolyzed to its corresponding cyclopropenone in hot,aqueous base, which is subsequently chlorinated to obtain 2. Tounderscore the accessibility of these materials, we note that themonomers are obtained by simple purification techniques. Using thisprocess, we prepared multigram quantities of 2 incorporating threedifferent secondary amines, as depicted in FIG. 5 (bottom). Importantly,the chemistry in FIG. 5 is highly amenable to a wide range ofnucleophilic secondary amines incorporating a variety of functionalgroups, including elements of asymmetry. Dicyclohexylamine,diisopropylamine and morpholine were specifically chosen forexamination, given that they differ significantly in their degrees ofhydrophilicity and steric hindrance.

The synthesis of the CPR monomers from the precursor (2) was readilyachieved in 10-20 g quantities. The chlorinated 1-position of 2 ishighly susceptible to addition of a secondary amine bearing apolymerisable unit, such as compound 5 (FIG. 5). A styrene-basedpolymerisable group was chosen as it is a well-behaved building block inpolymer chemistry, and its hydrophobicity relative to the CP ion moietycould stabilize an emulsion of the type used in nanoparticle synthesis.Other polymerisable moieties should yield functional monomers as well.

Example 9 Polymer Synthesis and Characterization

The three chosen monomers (CPCy, CPiP and CPMo, FIG. 5) were polymerizedby RAFT in multigram quantities yielding linear polymers (PCPCy, PCPiPand PCPMo, respectively, FIG. 6). PCPCy was purified through triturationinto 1,4-dioxane from CH₂Cl₂ with 88% recovered yield. PCPiP wasprecipitated from acetone or CH₂Cl₂ into cold ethyl acetate with 70%recovered yield. Due to their solubility in water, both PCPiP and PCPMocan be purified by dialysis. Purification of PCPMo resulted in a 51%recovered yield. Each of these polymers was isolated as a powder, andPCPiP and PCPMo were observed to be extremely hygroscopic. Throughend-group analysis of the ¹H nuclear magnetic resonance (NMR) spectra,we calculated the degree of polymerization (DP) and molecular mass ofeach of the homopolymers (Table 1). Due to the cationic nature of the CPgroups, polymers (and copolymers) cannot be characterized using sizeexclusion chromatography eluted with organic solvents, as the polymersadhere to the column. An attempt was made to characterise the dispersity(Ð) of the hydrophilic homopolymers (PCPiP and PCPMo) on anacetate-buffered aqueous size exclusion chromatography; however, onlyPCPMo successfully eluted owing to its greater hydrophilicity (FIG. 7,Table 2). The ≃ of PCPMo was determined to be 1.3, but we note that thisvalue may not accurately reflect the DP control, given that thepolyelectrolyte may still be interacting with the column as it iseluted. We note that the synthetic accessibility of these variousCP-based polymers is straightforward and highly efficient, rivallingthat of ammonium, phosphonium and imidazolium polymers (Hemp et al.2013, Yuan et al. 2011, Wang et al. 2007, Texter et al. 2012).

As expected, a significant relationship was observed between the natureof the amino substituent and the physical properties of the resultanthomopolymer. It was observed that the decomposition temperature(T_(dec)), glass transition temperature (T_(g)) and solubility of thehomopolymers varied as a function of substituent (Table 1). Throughcharacterization by thermo-gravimetric analysis we found that theT_(dec) of the homopolymers increased as the amino substituents becameless sterically hindered. Of particular note, PCPMo decomposed at 310°C., which is comparable to the T_(dec) of imidazolium-based polymers(Sudre et al. 2013). Differential scanning calorimetry was performed toidentify the T_(g) for the homopolymers, as ion-conducting membranes arefrequently melt-processed. Both PCPCy and PCPiP have no observable T_(g)before decomposition, but PCPMo exhibited a T_(g) of 160° C. Previousreports have revealed a connection between the nature of the counterionand the accessible temperature window; replacement of the chloride withan alternative, typically bulkier counterion is expected to increase theT_(dec) while decreasing the T (Curnow et al. 2011, Sudre et al. 2013,Weber et al. 2011). Importantly, however, the data clearly demonstrate asimilar relationship between alkyl chain identity and observed T_(dec)and T_(g); thus, by modifying the CP substituents, one can significantlybroaden the temperature window in which these materials are processable,without the need to adjust the counterion. In addition, solubility ofPCPR homopolymers is highly dependent on amino substituents, againreflecting the influence of building block composition on macromolecularproperties. Characterization of the homopolymers, including thermal dataand solubility information, is summarized in Table 1.

Statistical copolymers were readily synthesized by RAFT, using styreneand CPR monomers, P(S-stat-CPR). When styrene was copolymerized witheach monomer in a 1:1 mole ratio, we observed some disparities in thepercent incorporation of functional CP monomers in the resultingcopolymer. For CPCy, CPiP and CPMo, the degree of incorporation was 50%,48%, and 45%, respectively.

Considering the ability to copolymerize styrene and CPR monomers,cationic nanoparticles based on the CPiP monomer were synthesized viasurfactant-free emulsion polymerization. Many traditional strategiesrely on the use of surfactants or additional solvents (Ramos et al.2013) to obtain sub-100 nm cationic particles. By simply mixing styreneand CPiP at various weight percent values (1, 2.5, 5, 10 and 20% ofCPiP) and using a thermally activated radical initiator (V-50), we wereable to obtain particles ranging from 30 to 90 nm (as characterized bydynamic light scattering, FIG. 8). Higher loadings of CPiP compared withstyrene resulted in smaller, albeit more disperse, particles. FIG. 6shows the scanning electron microscope image of nanoparticles made from5% CPiP/95% styrene. The average diameter obtained by dynamic lightscattering was found to be 50 nm. Furthermore, the particles that formstable dispersions as the zeta potential of the 5% CPiP nanoparticleswas found to remain above 30 mV over the range of >10 pH units (FIG. 8).As a control, particles synthesized with styrene only (without anysurfactants or CPR monomers) were much larger and exhibited a bimodalsize distribution (FIG. 8). These data demonstrate that the CPiP monomereffectively stabilizes oil-in-water droplets, and that the charge ispresent on the particle surface. A more detailed study of this behaviorwill follow, including the incorporation of other CPR monomers intocationic nanoparticles. In general, the ability to make chargednanoparticles in a surfactant-free, large-scale process could havefar-reaching potential towards interfacial additives and biologicalapplications (Rothberg et al. 2011, Nederberg et al. 2011).

While the CPR monomers were successfully copolymerized to makestatistical polymers and nanoparticles, the library of CPR-basedmacromolecules was augmented with block copolyelectrolytes (BCPEs).Block copolymers PS-b-PCPR(CP mol %) were synthesized by growing styreneonto PCPR macro-chain transfer agents (macro-CTA). By varying the DP ofthe polystyrene block, we effectively controlled the different molefractions of the CP functional block. We note that block copolymersPS-b-PCPR could also be obtained by the reverse process of growing thefunctional monomer CPR onto polystyrene macro-CTAs.

Referring to Table 1, as the size and hydrophobicity of the alkyl chainsdecreased from PCPCy to PCPMo, conversion of the monomers becamenoticeably lower and T_(dec) was found to increase. PCPMo was found tohave a T_(g) of 160° C. Solubilities also depended on the hydrophilicityof the alkyl chains.

TABLE 1 Characterization of PCPR homopolymers. Solubilities^(b) SampleMM/kg mol⁻¹ DP T_(dec) T_(g) ^(a) CHCl₃ CH₂Cl₂ ROH^(c) H₂O THF PCPCy 3560 160° C. N/A ✓ ✓ ✓

PCPiP 17 40 225° C. N/A ✓ ✓ ✓ ✓

PCPMo 29 75 310° C. 160° C.

✓ ✓

^(a)Both PCPCy and PCPiP decomposed before reaching any recordableT_(g). ^(b)All homopolymers are soluble in DMF and DMSO and insoluble inhexanes, ethyl acetate, and diethyl ether. ^(c)ROH = methanol andethanol. Only PCPMo was not soluble in isopropanol. Note: ✓ meanssoluble and 

 is insoluble.

TABLE 2 SEC data for PCPMo (see FIG. 7). MM Mn MP Dispersity Peak(Daltons) (Daltons) (Daltons) ( 

 ) Name RT Area % Area Height 4587 3422 4036 1.340446 Broad 13.0941762186 100.00 25897 MM = mass average molecular mass. Mn = numberaverage molecular mass. MP = molecular mass at the peak maximum. RT =retention time.

Example 10 Morphology of BCPEs

After synthesizing block copolymers of various compositions, wecharacterized the morphology of bulk films comprising variousCPR-building blocks. Recent studies suggest that nanostructured BCPEshave broad implications in materials chemistry, specifically for fuelcells and batteries, if they undergo microphase segregation. Forexample, Ye et al. recently reported that BCPEs with a lamellarmorphology conduct ions more effectively than cationic homopolymers, aswater and ions confined within nanochannels may accelerate transport (Yeet al. 2013). Computational studies from Olvera de la Cruz and coworkerssuggest this effect may be enhanced if the conducting path is acontinuous, percolating structure (Sing et al. 2014); a microphasesegregated morphology of charged and neutral blocks observed inion-containing block copolymers (Park et al. 2007). With this in mind,block copolymer samples were characterized by small-angle X-rayscattering (SAXS) and TEM to understand microphase segregation inPCPR-containing BCPEs.

In FIG. 9 and FIG. 10, we show SAXS (Alexander et al. 2010) profiles ofthree representative diblock copolymers. The primary scattering peaksseen in each sample (indicated by filled triangles) is attributed tomicrophase separation. The scattering profile of PS-b-PCPMo(35) containsa higher-order peak at q=3q*. This suggests the presence of a symmetriclamellar phase. The scattering profiles of the other polymers containonly one peak, which indicates a lack of long-range order. The domainspacing, d, of the microphase separated diblock copolymers is calculatedby the equation d=2π/q*. The domain spacing values corresponding to eachdiblock copolymer are given in Table 3. As expected, d-spacing increaseswith molecular mass and molar fraction of styrene. Next, the potentialapplication of CP-based polyelectrolytes in electrochemical devices wasprobed (Chen et al. 2010, Sing et al. 2014).

TABLE 3 Characterization of PS-b-PCPR (CP mol %) block copolymers CP %CP % by SAXS domain Sample Name MM/kg mol⁻¹ by DP MM spacing (nm)PS-b-PCPCy(45) 40 45% 80% 15 PS-b-PCPCy(30) 50 30% 70% 18 PS-b-PCPiP(50)20 50% 80% 18 PS-b-PCPiP(30) 27 30% 60% 24 PS-b-PCPiP(20) 30 20% 50% 31PS-b-PCPMo(50) 38 50% 80% 26 PS-b-PCPMo(35) 42 35% 70% 28 CP,cyclopropenium; DP, degree of polymerization; NMR; nuclear magneticresonance; SAXS, small-angle X-ray scattering Block copolymers weresynthesized by the addition of styrene to the three homopolymers, anddomain spacing was calculated by SAXS Molecular mass (MM) was determinedby ¹H NMR spectroscopy.

Ion conductivity experiments were performed on PS-b-PCPiP(20) usingelectrochemical impedance spectroscopy. As conductivity is closelyrelated to morphology, SAXS experiments were complemented withtransmission electron microscopy (TEM). A PS-b-PCPiP(20) sample (dropcast, no annealing) was microtomed and imaged by TEM (FIG. 11a,b ). Evenwithout staining, microphase segregation (cylindrical morphology) wasclearly observed (FIG. 12). Staining with RuO₄ vapor for 2 minpreferentially stains the cationic block and helps to visualize theinternal structure. The electron micrographs obtained (FIG. 11a,b ) showhexagonally packed cylinders in different orientations. The domainspacing by TEM was 29 nm, which is consistent with the domain spacingdetermined by SAXS (31 nm; see Table 3). The lighter color of thecylinders with respect to the matrix in FIG. 11a,b indicates that PScylinders are embedded in a PCPiP matrix. The stained PCPiP blockscatters more electrons, and therefore appears darker by TEM (see FIG.12). The non-functionalized PS cylinders in FIG. 11a,b occupy a verylarge fraction of the image because the mole fraction of the functionalblock in this polymer is only 20%. The continuous nature of theconducting phase matrix observed in charged diblock copolymers isexpected to facilitate ion transport (Alexander et al. 2010), and isconsistent with the ideal percolating structure found by computationalmodeling (Sing et al. 2014).

The in-plane conductivity, σ, of PS-b-PCPiP(20) equilibrated in humidair with 90% relative humidity (RH) was measured as a function ofincreasing temperature from 25 to 65° C. (FIG. 11c ). To ensureequilibration, samples were initially annealed for 1 week at 90% RH at25° C. and for 48 h at each subsequent temperature of interest. Thestraight line in FIG. 11c is the least-squares fit through theequilibrated conductivity data at each temperature value.

In principle, the change in conductivity with temperature, shown in FIG.11c , could either be due to changes in the mobility of chloride ions orto a change in ion concentration in the membrane. The fact that ionconcentration in the membranes is constant indicates that the slope ofthe line provides an estimate of the activation energy for transport ofchloride ions through the membrane (Arrhenius law). The estimatedactivation energy for this system is 25 kJ mol⁻¹. This value iscomparable to that reported previously for the imidazolium-containingdiblock copolymer analogue in water,poly(styrene-b-4-vinylbenzyltri-methyl imidazolium chloride)(PS-b-PIm(35)), 27 kJ mol⁻¹ (Sudre et al. 2013). However, at roomtemperature, the conductivity of the PS-b-PCPiP (20) polymer(ion-exchange capacity, IEC=1.3 meq g⁻¹) is rather high, 0.004 S cm⁻¹,considering the low water uptake, λ_(w)=7, of this membrane (λ_(w) isthe number of water molecules per chloride ion in the membrane). Thisvalue of λ_(w) is four times lower than the value obtained forPS-b-PIm(35) immersed in water, for the same conductivity λ_(w)=30,σ=0.004 S cm⁻¹), and higher IEC (2.1 meq g⁻¹) (Sudre et al. 2013). Theseresults indicate that the CP-based polyelectrolytes of the presentinvention conduct ions more effectively than the optimized membranesfrom imidazolium-containing polymers, with a minimum amount of waterpresent. Further tuning of the functional groups, backbone structure andmorphology is expected to result in polyelectrolytes with exceptionallyhigh ion conductivities (Schmidt-Rohr et al. 2008, Choi et al. 2013,Hoarfrost et al. 2012, Ye et al. 2012).

In conclusion, a new family of electron-rich cationic polyelectrolytesbased on the CP ion building block was discovered. The robust, efficientand orthogonal chemistry to synthesize the monomers provides facileaccess to a variety of polymers by RAFT and to well-defined cationicnanoparticles by surfactant-free emulsion polymerization. Thenanoparticles exhibit high charge density on the surface and stabilityover a wide range of pH values. The family of linear polymers ischaracterized by widely variable physical properties, which are highlydependent on the amino substituents flanking the aromatic cation.Through TEM and SAXS measurements, we observed microphase segregation inbulk samples of the BCPE. In diblock copolymers, the domain spacingincreased with increasing styrene content (the length of the functionalblock was fixed). Compared with imidazolium analogues, CP-based BCPEsshow superior properties as ion conductive materials, and furtheroptimization should lead to improved performance. Future studies will beaimed at probing the structure-property relationships of these materialsby expanding our PCPR library through adjustment of the polymerbackbone, modular functional groups, block copolymer composition and CPcounterion. Moreover, other CPR monomers will be incorporated intonanoparticles via the one-pot emulsion polymerization to assess theirefficacy in various biomedical applications and membrane technologies.With such modularity, this new class of CP-based polyelectrolytes offersa wealth of functionality that translates to significant potentialacross a broad array of applications.

Example 11 Material and Methods for Examples 8-10

Materials and Reactions

All materials were purchased from Sigma Aldrich and were used withoutfurther purification except as noted below. Methylene chloride (CH₂Cl₂),tetrahydrofuran (THF), and N,N-dimethylformamide (DMF) were dried usinga J.C. Meyer solvent purification system. Styrene was filtered throughbasic alumina to remove radical inhibitor before use in polymerizations.Deuterated solvents for NMR were purchased from Cambridge IsotopeLaboratories, Inc. Eluents for column chromatography were HPLC grade andpurchased from Fisher Scientific.

All reactions were performed open to the atmosphere, unless otherwisenoted. Organic solutions were concentrated by use of a Buchi rotaryevaporator. All polymerizations were carried out with temperaturecontrol under vacuum in flame-sealed ampoules. Chemical shifts are givenin ppm relative to the signal from residual non-deuterated solvent.¹H-NMR and ¹³C-NMR spectra were recorded in CDCl₃ (except where noted)on Bruker DRX-300, DRX-400 or DRX-500 spectrometers. Data for ¹H NMR arereported as follows: chemical shift (δ ppm), multiplicity (s=singlet, brs=broad singlet, d=doublet, t=triplet, dd=doublet of doublets,dt=doublet of triplets, q=quartet, hept=heptet, m=multiplet), couplingconstant (Hz), integration, and assignment. Data for ¹³C are reported interms of chemical shift. High-resolution mass spectra were obtained fromthe Columbia University Mass Spectrometry Facility on a JEOL JMSHX110 HFmass spectrometer using FAB+ ionization mode. Low-resolution massspectrometry (LRMS) was performed on a JEOL JMS-LCmate liquidchromatography spectrometer system using APCI+ ionization technique.

Thin layer chromatography (TLC) was performed using Teledyne Silica gel60 F254 plates and viewed under UV light. Flash column chromatographywas performed using Teledyne Ultra Pure Silica Gel (230-400 mesh) on aTeledyne Isco Combiflash Rf.

Size Exclusion Chromatography (SEC)

PCPMo was characterized to quantify its molecular mass dispersity (Ð) ona Waters Alliance 2695 separation module equipped with a PL-aquagel-OH 8micron Mixed-M column (300×7.5 mm), a Waters 2998 Photodiode ArrayDetector, and a Waters 2414 Refractrometer Detector. Sodium acetatebuffer (0.3 M) with 20 vol % methanol was used as the eluent at a flowrate of 0.7 mL min⁻¹. Poly(ethylene glycol) standards were used forcalibration.

Thermogravimetric Analysis (TGA)

Thermogravimetric analysis was performed on a Perkin-Elmer Pyris 1 TGAfrom ambient temperature to 600° C. at a rate of 10° C. min⁻¹. Polymersamples were dried under high vacuum overnight prior to measurement, anddecomposition temperatures were recorded at 5% mass loss.

Differential Scanning Calorimetry (DSC)

Differential Scanning Calorimetry (DSC) was performed on a TAInstruments DSC Q2000 fitted with a RCS90 refrigerated cooling system todetermine the glass transition temperatures. DSC measurements were takenat a sampling rate of 10° C. min⁻¹ in the temperature range of 0° C. to200° C.

Dynamic Light Scattering (DLS)

Particle size, polydispersity, and electrophoretic mobility weremeasured using a Möbiuζ dynamic light scattering instrument and Dynamicssoftware from Wyatt Technology (Santa Barbara, Calif.). Particle sizeand polydispersity were calculated via the Regularization fit of thecorrelation function of the Quasi-elastic Light Scattering (QELS) data.Each measurement contained 10 acquisitions and at least 3 measurementswere performed. The reported radii or diameters are the average of thosemeasurements. Zeta potential was calculated according to theSmoluchowski approximation and reported values are the averaged resultof 5 acquisitions from each of the 31 detectors in the MassivelyParallel Phase Amplitude Light Scattering (MP-PALS) detector array.Measurements were run in MilliQ water at neutral pH unless otherwisenoted. Samples were passed through a 1.6 μm glass filter (Whatman) priorto measurement to remove only large aggregates and dust.

Scanning Electron Microscopy (SEM)

Scanning electron microscopy (SEM) was performed on a JEOL7001 FLV at3.0 to 10.0 keV. Particles were deposited on a silica wafer fromsolution, and imaged without sputter coating. Particle sizes measured bySEM were determined using ImageJ software by manually counting at least50 particles.

Quantification of Water Uptake

Water uptake of the polymer membrane was measured in ahumidity-controlled environmental chamber (Espec). A small piece ofwater-equilibrated membrane was placed in a quartz pan which was hookedon the end of a quartz spring (Deerslayer) in the humidity chamber. Themembrane was equilibrated at room temperature at 90% relative humidityfor 48 hr. The mass of the hydrated film was obtained by measuringspring length through a port on the wall of the humidity chamber by acathetometer equipped with an optical zoom telescope located outside thechamber. Care was taken to minimize the time when the port was opened(typically 10 s). The spring was calibrated with standard masses atexperimental temperature and relative humidity in the chamber before use(spring constant was about 0.5 mN mm⁻¹). Dry mass of humidair-equilibrated membrane was measured following the same procedure asdescribed above. The degree of hydration, λ_(w), defined as the moles ofwater per mole of cationic groups in the membrane, is calculated usingequation (1):

$\begin{matrix}{\lambda_{W} = {\frac{\left\lbrack {H_{2}O} \right\rbrack}{\lbrack{CP}\rbrack} = {\frac{{{hydrated}\mspace{14mu}{film}\mspace{14mu}{weight}} - {{dry}\mspace{14mu}{film}\mspace{14mu}{weight}}}{{dry}\mspace{14mu}{film}\mspace{14mu}{weight}} \times \frac{M_{CP} + {\left( {x_{CP}^{- 1} - 1} \right)M_{S}}}{M_{W}}}}} & (1)\end{matrix}$

where the molar mass of water and of the styrene (S) and cyclopropenium(CP) monomers are M_(W)=18.02 g mol⁻¹, M_(S)=104.15 g mol⁻¹ andM_(CP)=419 g mol⁻¹.

Small-Angle X-Ray Scattering

Thick polymer samples (1 nun) were prepared by pressing the powder intoa teflon washer. Synchrotron SAXS measurements were performed using the7.3.3 beamline at the Advanced Light Source (ALS, Lawrence BerkeleyNational Laboratory). The wavelength 2λ of the incident X-ray beam was0.124 nm (Δλ/λ=10⁻⁴) and a sample-to-detector distance of 4 m. Theresulting two-dimensional scattering data were averaged azimuthally toobtain intensity versus magnitude of the scattering wave vector q (q=4πsin(θ/2)/λ, where θ is the scattering angle). All of the scatteringprofiles were azimuthally symmetric. The scattering data were correctedfor the detector dark current and the scattering from air and Kaptonwindows. In-plane chloride conductivity of hydrated membranes withdimensions 2 cm×1 cm×450 μm was measured by AC impedance spectroscopyusing platinum electrodes in the standard four probe configuration usinga BekkTech sample clamp.

Electrochemical Impedance Spectroscopy

Polymer films of PS-b-PCPiP(20) were prepared by drop casting a 100 mgml⁻¹ solution of polymer onto a clean Teflon substrate. In-planechloride conductivity of a hydrated membrane composed of PS-b-PCP1P(20)(calculated molecular mass=31 KDa, DP=174) with dimensions 2 cm×1 cm×450μm was measured by AC impedance spectroscopy using platinum electrodesin the standard four probe configuration using a BekkTech sample clamp.Conductivities were collected under humidified conditions, andtemperature and RH were controlled by an environmental chamber(Qualitest). Data were collected using 10 mV amplitude over a frequencyrange of 1 Hz-10 MHz. Separate experiments were conducted to ensure thatthe response of the sample was linear in this window. Samples wereannealed at the temperature of interest for 24-48 h until the measuredimpedance did not change. Conductivity, σ, is given by equation (1):σ=w/rSwhere S is the cross-sectional area of sample film, r is the interceptof the Nyquist semi-circle on the real axis (Ω) and w is the distancebetween the inner platinum electrodes.Transmission Electron Microscopy

Films of PS-b-PCP1P(20) (calculated molecular mass=33.4 KDa, DP=200)were prepared by drop casting a 100 mg ml⁻¹ solution of polymer onto aclean Teflon substrate. After allowing to dry for 24 h, the film wassectioned with Leica UltraCut 6 ultramicrotome at −40° C., nominalthickness 70 nm using a Diatome Cryo 35° diamond knife. Sections wereplaced on 300 mesh copper grids with homemade lacey carbon film on top.The sections were stained with RuO₄ vapor for 2 min, whichpreferentially stained the PCPiP block. Sections were imaged with FEITecnai F20 TEM operated at 200 kV. Images were analysed using ImageJ1.48v software.

Example 12 Alternative Synthesis Pathways Synthesis ofN-methyl-1-(2,3-bis(dicyclohexylamino)cyclopropenium)-4-vinylbenzylaminechloride (CPCy)

To a dry round bottom flask of2,3-bis(di-cyclohexylamino)-1-chlorocyclopropenium chloride (22.1 g,47.3 mmol, 1.0 equiv) under argon was added CH₂Cl₂ (150 ml) andtriethylamine (6.54 ml, 47.3 mmol, 1.0 equiv).N-Methyl-4-vinylbenzylamine (7.74 g, 47.3 mmol and 1.0 equiv) was thenslowly added to the solution and the reaction was stirred overnight.CH₂Cl₂ (700 ml) was added and the mixture was washed with 1 M HCl (3×200ml) and brine (1×200 ml), dried with anhydrous sodium sulfate andconcentrated in vacuo to yield a crude solid. The crude product waspurified with silica gel chromatography (EtOAc then 5% iPrOH in CH₂Cl₂)to yield an off-white solid (23.5 g, 40.6 mmol, 86% yield). Monomerswere characterized by ¹H and ¹³C NMR (see FIGS. 13-18), and all newcompounds were characterized by NMR and mass spectrometry.

Sample Synthesis of PCPR: Synthesis of PCPCy

To a dry 20 ml scintillation vial, CPCy (6.0 g, 10.4 mmol, 60.0 equiv),methyl 2-(phenylcarbonothioylthio)-2-phenylacetate (52.3 mg, 1.73 mmol,1.0 equiv), AIBN (4.3 mg, 0.26 mmol, 0.15 equiv) and DMF (6.0 ml) wereadded and vortexed to form a homogenous solution. This solution wastransferred to a flame-dried ampule. After 4 freeze-pump-thaw cycles,the ampule was sealed under vacuum. The polymerization was run for 12 hat 80° C. with vigorous stirring. The reaction mixture was precipitatedfrom CH₂Cl₂ into 1,4-dioxane three times to remove monomer. The polymerwas then precipitated an additional three times into hexanes to removeresidual 1,4-dioxane. Drying in vacuo yielded the pure polymer as a pinkpowder (5.3 g, 86% yield). Homopolymers were characterized by ¹H NMR(see FIGS. 19-21).

Synthesis of 2,3-bis(dicyclohexylamino)-1-chlorocyclopropenium chloride

Dicyclohexylamine (168 mL, 804.8 mmol, 6.0 equiv) was slowly added to asolution of pentachlorocyclopropane (Tobey et al. 1966) (30.0 g, 140.0mmol, 1.0 equiv) in CH₂Cl₂ (1500 mL) in a 3 L round bottom flask. Awhite precipitate formed as the reaction mixture was stirred for afurther 48 hr at room temperature. The solution was washed with 1M HCl(3×500 mL), dried with anhydrous sodium sulfate, and concentrated invacuo to yield an off-white solid. This solid was triturated with hotethyl acetate to give the title product (60 g, 130 mmol, 92%). ¹H NMR(500 MHz, CDCl₃) b 3.75 (m, 2H, NCyH), 3.40 (m, 2H, NCyH), 1.10-2.20 (m,40H, CyH). ¹³C NMR (125 MHz, CDCl₃) δ 131.6, 93.1, 65.2, 56.3, 32.1,30.2, 24.9, 24.7, 24.0, 23.8. HRMS (FAB+) m/z=431.3418 calcd forC₂₇H₄₄N₂Cl [M]⁺ 431.32.

Synthesis of 2,3-bis(diisopropylamino)-1-chlorocyclopropenium chloride

Pentachlorocyclopropane (5.20 g, 22.8 mmol, 1.0 equiv) was added to 230mL of CH₂Cl₂ in a 500 mL dry round bottom flask equipped with a stirbar. To this solution, diisopropylamine (18.48 g, 182.6 mmol, 8.0 equiv)was slowly added and allowed to stir under argon at room temperatureovernight. Solvent was removed from the reaction mixture leaving acrude, brown sandy-looking mixture of the desired product inquantitative yield and 3-4 equivalents of the corresponding ammoniumsalt. This crude mixture was used in subsequent steps without furtherpurification. ¹H NMR (400 MHz, CDCl₃) δ 4.28 (hept, J=6.7 Hz, 2H,C₃(NCH(CH₃)₂CH(CH₃)₂)₂), 3.89 (hept, J=6.8 Hz, 2H,C₃(NCH(CH₃)₂CH(CH₃)₂)₂), 1.45 (m, 24H, C₃(N(CH(CH₃)₂)₂)₂). ¹³C NMR (125MHz, CDCl₃) δ 132.0, 117.8, 93.3, 58.1, 48.6, 47.1, 22.6, 21.8, 20.9,18.9.

Synthesis of 2,3-bis(morpholino)-1-cyclopropenone

Morpholine (58.0 g, 665.7 mmol, 7.1 equiv) was slowly added to asolution of pentachlorocyclopropane (20.0 g, 93.3 mmol, 1.0 equiv) inCH₂Cl₂ (250 mL) in a 500 mL round bottom flask. The solution turnedorange, and a white precipitate formed as the reaction mixture wasstirred overnight at room temperature. The white solid was filtered offand the filtrate was concentrated in vacuo to a crude red solid. Water(100 mL) was used to dissolve this solid. A room temperature solution ofpotassium hydroxide (20 g, 356.4 mmol) in water (30 mL) was added to thesolution, which was heated to 65° C. for one hr. The reaction solutionwas allowed to cool and water was then removed by rotary evaporation.The resulting solid was washed with CH₂Cl₂ (500 mL) and any remainingsolid was filtered off. The organic solution was dried with anhydroussodium sulfate and concentrated in vacuo to yield a crude orange solid.The crude material was purified by silica gel chromatography (10% MeOHin EtOAc) to yield the title product as an off-white solid (8.9 g, 39.7mmol, 42% two-step yield). Note: the temperature of the rotovap was keptat 30° C. or cooler, and extended exposure to methanol will decomposethe title product. ¹H NMR (400 MHz, CDCl₃) δ 3.73 (m, 8H, NCH₂CH₂O),3.34 (m, 8H, NCH₂CH₂O). ¹³C NMR (125 MHz, CDCl₃) δ 134.8, 120.3, 66.1,49.3. HRMS (FAB+) m/z=225.1243 calcd for C₁₁H₁₇N₂O₃ [M]⁺ 225.12.

Synthesis of 2,3-bis(morpholino)-1-chlorocyclopropenium chloride

Oxalyl chloride (6.86 mL, 79.4 mmol, 2.0 equiv) was slowly added to a 0°C. solution of 2,3-bis(morpholino)-1-cyclopropenone (8.9 g, 39.7 mmol,1.0 equiv) in CH₂Cl₂ (250 mL) under argon. The solution was warmed toroom temperature and left to react for one hr. The product was dried invacuo to yield a sufficiently pure black solid in quantitative yield(11.0 g, 39.7 mmol). ¹H NMR (400 MHz, CDCl₃) δ 4.05 (m, 4H,N(HCH—CHH)₂O), 3.90 (dt, J=20.2, 4.5 Hz, 8H, N(HCH—CHH)₂O) 3.66 (m, 4H,N(HCH—CHH)₂O).

Synthesis of N-methyl-4-vinylbenzylamine

Vinylbenzyl chloride (7.5 g, 49.3 mmol, 1 equiv) was added to a 1 Lround bottom flask equipped with a stir bar. Methylamine solution (8.0Min ethanol, 101.1 mL, 15 equiv) was added to the sealed flask, and anoutlet was used to relieve pressure. THF (330 mL) was added to dilutethe reaction mixture such that the concentration of vinylbenzyl chloridewas 0.10M. The flask was filled with argon and sealed with a septumsecured with copper wire. The contents of the reaction flask wereallowed to stir at 45° C. for 24 hr. Solvent was subsequently removed byrotary evaporation, and the crude product was dissolved in 250 mL ofCH₂Cl₂ and transferred to a 1 L separatory funnel. This solution waswashed 3× with 1.0M NaOH, 1× with DI water, and 1× with brine, and driedover magnesium sulfate. Removal of solvent by rotary evaporation yieldedthe title product as yellow oil. ¹H NMR was used to determine purity.(6.82 g, 46.4 mmol, 94% yield, 90% purity). The oil was stored at 0° C.and was used without further purification. ¹H NMR (400 MHz, CDCl₃) δ7.33 (m, 4H, ArH), 6.71 (dd, J=17.6, 10.9 Hz, 1H, H₂C═CHAr), 5.73 (dd,J=17.6, 1.0 Hz, 1H, H₂C═CHAr), 5.21 (dd, J=10.9, 2.3 Hz, 1H, H₂C═CHAr),3.73 (s, 2H, ArCH₂N), 2.45 (s, 3H, NCH₃).

Procedures for Synthesis of CPR Monomers

Characterization ofN-methyl-1-(2,3-bis(dicyclohexylamino)cyclopropenium)-4-vinylbenzylaminechloride (CPCy)

¹H NMR (500 MHz, CDCl₃) δ 7.33 (m, 4H, ArH), 6.69 (dd, J=17.7, 10.9 Hz,1H, H₂C═CHAr), 5.74 (d, J=17.6 Hz, 1H, H₂C═CHAr), 5.25 (d, J=11.0 Hz,1H, H₂C═CHAr), 4.80 (s, 2H, ArCH₂N), 3.35 (m, 4H, NCyH), 3.22 (s, 3H,NCH₃), 1.00-1.90 (m, 40H, CyH). ¹³C NMR (125 MHz, CDCl₃) δ 137.4, 135.6,133.6, 126.8, 126.6, 119.0, 117.8, 114.3, 60.3, 57.5, 39.4, 31.7, 25.2,24.2. HRMS (FAB+) m/z=542.4333 calcd for C₃₇H₅₆N₃[M]⁺ 542.45.

Synthesis ofN-methyl-1-(2,3-bis(diisopropylamino)cyclopropenium)-4-vinylbenzylaminechloride (CPiP)

In a 1 L round bottom flask equipped with stir bar,2,3-bis(diisopropylamino)-1-chlorocyclopropenium chloride (26.23 g crudemixture, 38.0 mmol CP salt, 1.0 equiv) and triethylamine (11.5 g, 114.0mmol, 3.0 equiv) were dissolved in 420 mL of CH₂Cl₂ and put under anatmosphere of argon. N-Methyl-4-vinylbenzylamine (5.59 g, 38.0 mmol, 1.0equiv) was slowly added to the solution, which was stirred for 15 hr.The reaction mixture was poured into a 1 L separatory funnel and washedwith 1M HCl (3×200 mL), then DI water (1×200 mL), followed by brine(1×200 mL). The organic layer was collected and dried over magnesiumsulfate. Rotary evaporation yielded 20.0 g of a dark brown viscousliquid. This crude product was purified by silica gel chromatography,eluted first with 100% EtOAc, followed by a mixture of 5% increasing to20% MeOH in CH₂Cl₂. Collection of pure fractions, followed by removal ofsolvent by rotary evaporation yielded an amber oil (13.97 g, 33.3 mmol,88% yield)¹H NMR (400 MHz, CDCl₃) δ 7.44 (m, 2H, ArH), 7.25 (m, 2H,ArH), 6.69 (dd, J=17.6, 10.9 Hz, 1H, H₂C═CHAr), 5.78 (dd, J=17.6, 0.8Hz, 1H, H₂C═CHAr), 5.29 (dd, J=10.9, 0.8 Hz, 1H H₂C═CHAr), 4.82 (s, 2H,ArCH₂N), 3.90 (hept, 4H, C₃NCH(Me)₂), 3.24 (s, 3H, NCH₃), 1.00-1.90 (m,24H, NCH(CH₃)₂). ¹³C NMR (125 MHz, CDCl₃) δ 137.7, 135.9, 134.0, 127.1,126.9, 119.0, 116.9, 114.6, 57.9, 51.5, 39.8, 22.01. HRMS (FAB+)m/z=382.3241 calcd for C₂₅H₄₀N₃[M]⁺ 382.32.

Synthesis ofN-methyl-1-(2,3-Bis(morpholino)cyclopropenium)-4-vinylbenzylaminechloride (CPMo)

To a dry round bottom flask of2,3-bis(morpholino)-1-chlorocyclopropenium chloride (11.08 g, 39.7 mmol,1.0 equiv) under argon was added CH₂Cl₂ (150 mL) andN,N-diethylmethylamine (5.3 mL, 43.7 mmol, 1.1 equiv).N-Methyl-4-vinylbenzylamine (5.3 g, 35.7 mmol, 0.9 equiv) was thenslowly added to solution, and the reaction was left overnight. The crudeproduct was concentrated in vacuo and dissolved in 250 mL of CHCl₃:iPrOH(2:1). The solution was extracted with water (2×100 mL), dried withanhydrous sodium sulfate, and concentrated in vacuo to yield a crudesolid. A portion of the product is lost in the aqueous wash. The crudeproduct was purified with silica gel chromatography (20% MeOH in CH₂Cl₂)to yield a dark solid (10.0 g, 25.6 mmol, 59% yield). ¹H NMR (500 MHz,CDCl₃) δ 7.44 (m, 2H, ArH), 7.24 (m, 2H, ArH), 6.70 (dd, J=17.7, 11.0Hz, 1H, H₂C═CHAr), 5.76 (dd, J=17.9, 1.7 Hz, 2H, H₂C═CHAr), 5.28 (dd,J=10.9, 1.5 Hz, 2H, H₂C═CHAr), 4.65 (s, 2H, ArCH₂N), 3.81 (m, 8H,NCH₂CH₂O), 3.54 (m, 8H, NCH₂CH₂O), 3.21 (s, 3H, NCH₃). ¹³C NMR (125 MHz,CDCl₃) δ 137.8, 135.9, 133.8, 127.0, 127.0, 118.8, 117.1, 114.7, 65.8,58.6, 50.0, 40.8. HRMS (FAB+) m/z=354.2171 calcd for C₂₁H₂₈N₃O₂ [M]⁺354.22.

Procedures for RAFT Homopolymerizations of PCPR

Characterization of PCPCy

¹H NMR (500 MHz, CDCl₃) δ 7.76-7.60 (b, 2H, —SC(ArH)S—), 7.51-6.00 (b,240H, ArH), 5.17-4.58 (b, 120H, ArCH₂N), 3.61-2.94 (b, 420H, NCyH,NCH₃), 2.05-0.75 (b, 2580H, CyH, ArCHCH₂).

Synthesis of PCPiP. CPiP

(3.5 g, 83.1 mmol, 50.0 equiv), MCPDB (50.2 mg, 1.66 mmol, 1.0 equiv),AIBN (0.54 mg, 0.033 mmol, 0.20 equiv), and N,N-dimethylformamide (DMF)(0.60 mL) were added to a flame seal ampoule and vortexed to form ahomogenous solution. A stir bar was added to the ampoule, and after 4freeze-pump-thaw cycles to remove oxygen, the ampoule was sealed undervacuum. The polymerization was run for 2 hr 15 min at 100° C. Thereaction mixture was precipitated from CH₂Cl₂ into −78° C. ethyl acetate5 times to remove monomer. Drying in vacuo yielded the polymer as a pinkpowder (2.45 g, 70% yield). Alternatively, the reaction mixture could betransferred to a 3.5 k MWCO Spectrum labs dialysis bag to dialyze for 24hr in 1 L of water. ¹H NMR (500 MHz, CDCl₃) δ 7.06-6.45 (b, 166H, ArH),4.98-4.65 (b, 80H, ArCH₂N), 3.98-3.79 (b, 165H, C₃NCH(iPr)₂), 3.48 (s,3H, OCH₃), 1.67-1.27 (b, 1700H, iPrH, ArCHCH₂).

Synthesis of PCPMo

To a dry 20 mL scintillation vial, CPMo (7.0 g, 17.9 mmol, 700 equiv),MCPDB (54 mg, 0.179 mmol, 1.0 equiv), AIBN (4.4 mg, 0.0269 mmol, 0.15equiv), and DMF (7.0 mL) were added and vortexed to form a homogenoussolution. This solution was transferred to a flame-dried ampoule. After4 freeze-pump-thaw cycles, the ampoule was sealed under vacuum. Thepolymerization was run for 12 hr at 85° C. The reaction mixture was thentransferred into a 3.5 k MWCO Spectrum labs dialysis bag and left todialyze for 24 hr in 1 L of water. The water was changed five times inthis time. The resulting polymer solution was freeze-dried to yield thepure polymer as a brown solid (3.6 g, 51% yield). ¹H NMR (500 MHz,CD₃OD) b 7.90-7.74 (b, 2H, —SC(ArH)S—), 7.67-6.26 (b, 300H, ArH),4.77-4.46 (b, 150H, ArCH₂N), 3.87-3.62 (b, 600H, NCH₂CH₂O), 3.62-3.38(b, 600H, NCH₂CH₂O), 3.29-3.03 (b, 225H, NCH₃), 2.55-1.04 (b, 225H,ArCHCH₂).

Procedures for RAFT Block Polymerization of PS-b-PCPR

Synthesis of PS-b-PCPCy(45)

To a dry 20 mL scintillation vial, PCPCy (1.0 g, 0.029 mmol, 1.0 equiv),AIBN (7.0 mg, 4.3 mmol, 0.15 equiv), styrene (0.722 g, 6.93 mmol, 4equiv), and DMF (1.75 mL) were added and vortexed to form a homogenoussolution. This solution was transferred to a flame-dried ampoule. After4 freeze-pump-thaw cycles, the ampoule was sealed under vacuum. Thepolymerization was run for 12 hr at 80° C. The reaction mixture wasprecipitated from CH₂Cl₂ into hexanes 3 times. Drying in vacuo yieldedthe pure polymer as a pink powder (0.850 g, 70% yield). ¹H NMR (500 MHz,CDCl₃) δ 7.90-7.78 (b, 2H, —SC(ArH)S—), 7.51-6.04 (b, 600H, ArH),5.23-4.58 (b, 120H, ArCH₂N), 3.73-2.96 (b, 420H, NCyH, NCH₃), 2.05-0.75(b, 2800H, CyH, ArCHCH₂).

Synthesis of PS-b-PCPCy(30)

To a dry 20 mL scintillation vial, PCPCy (1.0 g, 0.029 mmol, 1.0 equiv),AIBN (7.0 mg, 4.3 mmol, 0.15 equiv), styrene (1.08 g, 10.4 mmol, 6equiv), and DMF (1.75 mL) were added and vortexed to form a homogenoussolution. This solution was transferred to a flame-dried ampoule. After4 freeze-pump-thaw cycles, the ampoule was sealed under vacuum. Thepolymerization was run for 12 hr at 80° C. The reaction mixture wasprecipitated from CH₂Cl₂ into hexanes 3 times. Drying in vacuo yieldedthe pure polymer as a pink powder (0.850 g, 60% yield). ¹H NMR (500 MHz,CDCl₃) δ 7.90-7.78 (b, 2H, —SC(ArH)S—), 7.51-6.04 (b, 940H, ArH),5.23-4.58 (b, 120H, ArCH₂N), 3.73-2.96 (b, 420H, NCyH, NCH₃), 2.05-0.75(b, 3180H, CyH, ArCHCH₂).

Synthesis of PS-b-PCPiP(50)

To a dry flame-seal ampoule with stir bar, PCPiP (226.5 mg, 0.012 mmol,1.0 equiv), AIBN (0.44 mg, 0.0027 mmol, 0.2 equiv), styrene (0.277 g,2.66 mmol, 200 equiv), and DMF (0.130 mL) were added and vortexed toform a homogenous solution. After 4 freeze-pump-thaw cycles, the ampoulewas sealed under vacuum. The polymerization was stirred vigorously for 8hr at 100° C. The reaction mixture was precipitated from CH₂Cl₂ into−78° C. ethyl acetate 3 times. Drying in vacuo yielded the pure polymeras a pale pink powder (0.240 g, 88% yield). ¹H NMR (500 MHz, CDCl₃) b7.07-6.46 (b, 314H, ArH), 5.11-4.59 (b, 80H, ArCH₂N), 4.11-3.74 (b,172H, C₃NCH(iPr)₂), 3.93-2.97 (b, 122H, NCH₃), 2.30-0.98 (b, 1600H,iPrH, ArCHCH₂).

Synthesis of PS-b-PCPiP(30)

To a dry flame-seal ampoule with stir bar, PCPiP (271 mg, 0.014 mmol,1.0 equiv), AIBN (0.52 mg, 0.0032 mmol, 0.2 equiv), styrene (0.414 g,3.99 mmol, 250 equiv), and DMF (0.240 mL) were added and vortexed toform a homogenous solution. After 4 freeze-pump-thaw cycles, the ampoulewas sealed under vacuum. The polymerization was stirred vigorously for24 hr at 100° C. The reaction mixture was precipitated from CH₂Cl₂ into−78° C. ethyl acetate 3 times. Drying in vacuo yielded the pure polymeras a pale pink powder (0.310 g, 65% yield). ¹H NMR (500 MHz, CDCl₃) b7.26-6.27 (b, 510H, ArH), 4.90-4.59 (b, 80H, ArCH₂N), 4.01-3.71 (b,167H, C₃NCH(iPr)₂), 3.34-2.95 (b, 118H, NCH₃), 2.10-1.10 (b, 1690H,iPrH, ArCHCH₂).

Synthesis of PS-b-PCPiP(20)

To a dry flame-seal ampoule with stir bar, PCPiP (230 mg, 0.012 mmol,1.0 equiv), AIBN (0.2 mg, 0.0012 mmol, 0.1 equiv), styrene (1.37 g, 13.2mmol, 1000 equiv), and DMF (0.460 mL) were added and vortexed to form ahomogenous solution. After 4 freeze-pump-thaw cycles, the ampoule wassealed under vacuum. The polymerization was stirred vigorously for 30 hrat 95° C. Such a large excess of styrene was used so the polymer wouldnot precipitate out of solution during the reaction. The reactionmixture was precipitated from CH₂Cl₂ into a −78° C. solution of 25%ethyl acetate in hexanes 3 times. Drying in vacuo yielded the purepolymer as a pale pink powder (0.270 g, 62% yield). ¹H NMR (400 MHz,CDCl₃) δ 7.26-6.24 (b, 900H, ArH), 4.95-4.59 (b, 80H, ArCH₂N), 4.01-3.77(b, 176H, C₃NCH(iPr)₂), 3.27-3.01 (b, 126H, NCH₃), 2.02-0.94 (b, 1590H,iPrH, ArCHCH₂).

Synthesis of PS-b-PCPMo(50)

To a dry 20 mL scintillation vial, PCPMo (0.700 g, 0.024 mmol, 1.0equiv), AIBN (0.59 mg, 0.0036 mmol, 0.15 equiv), styrene (0.75 g, 7.2mmol, 4 equiv), and DMF (2.5 mL) were added and vortexed to form ahomogenous solution. The large volume of DMF was necessary to totallydissolve PCPMo. This solution was transferred to a flame-dried ampoule.After 4 freeze-pump-thaw cycles, the ampoule was sealed under vacuum.The polymerization was run for 12 hr at 85° C. The reaction mixture wasprecipitated from CH₂Cl₂ into diethyl ether 2 times. Drying in vacuoyielded the pure polymer as a pink powder (0.820 g, 90% yield). ¹H NMR(500 MHz, (CD₃)₂SO) δ 7.86-7.71 (b, 2H, —SC(ArH)S—), 7.47-6.09 (b, 760H,ArH), 4.90-4.28 (b, 150H, ArCH₂N), 3.85-3.54 (b, 600H, NCH₂CH₂O),3.54-3.30 (b, 600H, NCH₂CH₂O), 3.22-2.86 (b, 225H, NCH₃), 2.15-1.12 (b,500H, ArCHCH₂).

Synthesis of PS-b-PCPMo(35)

To a dry 20 mL scintillation vial, PCPMo (0.900 g, 0.031 mmol, 1.0equiv), AIBN (0.76 mg, 0.0046 mmol, 0.15 equiv), styrene (2.3 g, 22.2mmol, 10 equiv), and DMF (8.0 mL) were added and vortexed to form ahomogenous solution. The large volume of DMF was necessary to totallydissolve PCPMo. This solution was transferred to a flame-dried ampoule.After 4 freeze-pump-thaw cycles, the ampoule was sealed under vacuum.The polymerization was run for 12 hr at 85° C. The reaction mixture wasprecipitated from CH₂Cl₂ into diethyl ether 2 times. Drying in vacuoyielded the pure polymer as a pink powder (1.19 g, 88% yield). ¹H NMR(500 MHz, (CD₃)₂SO) δ 7.86-7.71 (b, 2H, —SC(ArH)S—), 7.58-6.05 (b,1000H, ArH), 5.01-4.28 (b, 150H, ArCH₂N), 3.85-3.53 (b, 600H, NCH₂CH₂O),3.53-3.24 (b, 600H, NCH₂CH₂O), 3.21-2.57 (b, 225H, NCH₃), 2.23-1.08 (b,640H, ArCHCH₂).

Synthesis of PS-b-PCPMo(30)

To a dry 20 mL scintillation vial, PCPMo (0.900 g, 0.031 mmol, 1.0equiv), AIBN (0.76 mg, 0.0046 mmol, 0.15 equiv), styrene (4.0 g, 38.9mmol, 17 equiv), and DMF (11.25 mL) were added and vortexed to form ahomogenous solution. The large volume of DMF was necessary to totallydissolve PCPMo. This solution was transferred to a flame-dried ampoule.After 4 freeze-pump-thaw cycles, the ampoule was sealed under vacuum.The polymerization was run for 12 hr at 85° C. The reaction mixture wasprecipitated from CH₂Cl₂ into diethyl ether 2 times. Drying in vacuoyielded the pure polymer as a pink powder (1.19 g, 82% yield). ¹H NMR(500 MHz, (CD₃)₂SO) δ 7.86-7.71 (b, 2H, —SC(ArH)S—), 7.47-6.03 (b,1175H, ArH), 4.92-4.30 (b, 150H, ArCH₂N), 3.81-3.54 (b, 600H, NCH₂CH₂O),3.54-3.34 (b, 600H, NCH₂CH₂O), 3.21-2.92 (b, 225H, NCH₃), 2.21-0.92 (b,750H, ArCHCH₂).

Procedures for RAFT random copolymerization of P(S-r-CPR)

Synthesis of P(S-r-CPCy)

To a dry 20 mL scintillation vial, CPCy (1.00 g, 1.73 mmol, 50.0 equiv),styrene (0.180 g, 1.73 mmol, 50.0 equiv), MCPDB (10.5 mg, 0.0346 mmol,1.0 equiv), AIBN (0.852 mg, 0.00519 mmol, 0.15 equiv), and DMF (0.500mL) were added and vortexed to form a homogenous solution. This solutionwas transferred to a flame-dried ampoule. After 4 freeze-pump-thawcycles, the ampoule was sealed under vacuum. The polymerization was runfor 12 hr at 80° C. The reaction mixture was precipitated three timesinto ethyl acetate and once in hexanes. Drying in vacuo yielded the purepolymer as a pink powder (790 mg, 67% yield). Integration of the ¹H NMRshowed approximately 35 units of CPCy and 35 units of styrene (50% CPCyincorporation). ¹H NMR (500 MHz, CDCl₃) δ 7.89-7.69 (b, 2H, —SC(ArH)S—),7.39-6.04 (b, 600H, ArH), 5.09-4.42 (b, 120H, ArCH₂N), 3.60-2.89 (b,420H, NCyH, NCH₃), 2.09-0.77 (b, 2800H, CyH, ArCHCH₂).

Synthesis of P(S-r-CPiP)

To a dry, flame-seal ampoule with stir bar, CPiP (1.8 g, 4.24 mmol, 50equiv), styrene (0.446 g, 4.29 mmol, 50 equiv), AIBN (1.4 mg, 0.0086mmol, 0.1 equiv), 2-cyanopropan-2-yl benzodithioate (19 mg, 0.086, 1.0equiv) and DMF (0.233 mL) were added and vortexed to form a homogenoussolution. After 4 freeze-pump-thaw cycles, the ampoule was sealed undervacuum. The polymerization was stirred vigorously for 17 hr at 95° C.The reaction mixture was precipitated from CH₂Cl₂ into a −78° C.solution of 25% ethyl acetate in hexanes 3 times. Drying in vacuoyielded a pale pink powder composed of approximately 13 units of CPiPand 15 units of styrene (0.270 g, 62% yield, 47% incorporation of CPiP).¹H NMR (400 MHz, CDCl₃) δ 7.26-6.24 (b, 920H, ArH), 4.95-4.59 (b, 90H,ArCH₂N), 4.01-3.77 (b, 200H, C₃NCH(iPr)₂, 3.27-3.01 (b, 136H, NCH₃),2.02-0.94 (b, 1750H, iPrH, ArCHCH₂).

Synthesis of P(S-r-CPMo)

To a dry 20 mL scintillation vial, CPMo (0.500 g, 1.28 mmol, 50.0equiv), styrene (0.134 g, 1.28 mmol, 50.0 equiv), MCPDB (7.74 mg, 0.0256mmol, 1.0 equiv), AIBN (0.632 mg, 0.00385 mmol, 0.15 equiv), and DMF(0.500 mL) were added and vortexed to form a homogenous solution. Thissolution was transferred to a flame-dried ampoule. After 4freeze-pump-thaw cycles, the ampoule was sealed under vacuum. Thepolymerization was run for 12 hr at 90° C. The reaction mixture wasprecipitated once into −78° C. ethyl acetate to remove styrene. Theprecipitate was dissolved in water and transferred to a 1.0 k MWCOSpectrum Labs dialysis bag and left to dialyze for 24 hr in 1 L ofwater. The water was changed 5 times during this time. The resultingpolymer was freeze-dried to yield pure polymer as a brown solid (0.190g, 30% yield). Integration of the ¹H NMR showed about 25 units of CPMoand 30 units of styrene (45% CPMo incorporation). ¹H NMR (500 MHz,(CD₃)₂SO) δ 7.86-7.70 (b, 2H, —SC(ArH)S—), 7.56-6.18 (b, 1175H, ArH),4.90-4.23 (b, 150H, ArCH₂N), 3.93-3.53 (b, 600H, NCH₂CH₂O), 3.53-3.17(b, 600H, NCH₂CH₂O), 3.17-2.85 (b, 225H, NCH₃), 2.40-1.05 (b, 225H,ArCHCH₂).

Synthesis of Surfactant-Free Emulsion Particles

Particles were synthesized by following a general procedure that wasscaled accordingly using 1-20 wt. % CPiP (relative to styrene), styrene,2,2′-azobis(2-methylpropionamidine) dihydrochloride (V-50), and water.The final solution was scaled to 10 grams, with 10 wt. % monomercontent. First, CPiP was dissolved in styrene and initiator wasdissolved separately in 1 mL of water. The remaining volume of water wasadded to the monomer solution, and the V-50 solution was finally addedto the monomer suspension. The mixture was vortexed for 30 seconds. Thesolution was added to a two-neck flask fitted with a condenser andstirbar, and was sparged with N₂ for 10 minutes. The solution wasstirred at 70° C. for 6-16 hours.

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All documents cited in this application are hereby incorporated byreference as if recited in full herein.

Although illustrative embodiments of the present invention have beendescribed herein, it should be understood that the invention is notlimited to those described, and that various other changes ormodifications may be made by one skilled in the art without departingfrom the scope or spirit of the invention.

What is claimed is:
 1. A stable, polycationic compound made by a processfor incorporating a cyclopropenium ion into a polymeric systemcomprising contacting a functionalized cyclopropenium ion with afunctionalized compound capable of reacting with the functional group ofthe cyclopropenium ion for a period of time and under conditionssuitable for the functionalized cyclopropenium and the functionalizedcompound to react and form a polymeric system that comprises a stablecyclopropenium cation that remains positively charged at a high pH,wherein the functionalized cyclopropenium ion is a compound of formula:

wherein X₁R₁R₂ is Cl, Br, F or I, or N bonded to R₁ and R₂, X₂R₃R₂ isCl, Br, F or I, or N bonded to R₂ and R₃, and X₃R₃R₄ is Cl, Br, F or I,or N bonded to R₃ and R₄, wherein R₁₋₄ are independently selected fromthe group consisting of no atom, amino, aryl, heteroaryl, C₁₋₁₀alkoxy,C₂₋₁₀alkenyloxy, C₂₋₁₀alkynyloxy, C₁₋₁₀alkyl, C₃₋₁₀cycloalkyl,C₂₋₁₀alkenyl, C₃₋₁₀cycloalkenyl, C₂₋₁₀alkynyl, halogen, aryloxy,heteroaryloxy, C₂₋₁₀alkoxycarbonyl, C₁₋₁₀alkylthio, C₂₋₁₀alkenylthio,C₂₋₁₀alkynylthio, C₁₋₁₀alkylsulfonyl, C₁₋₁₀alkylsulfinyl,aryl-C₁₋₁₀alkyl, heteroaryl-C₁₋₁₀alkyl, aryl-C₁₋₁₀heteroalkyl,heteroaryl-C₁₋₁₀heteroalkyl, a phosphorous group, a silicon group and aboron group, wherein R₁ and R₂ or R₃ and R₄ are optionally combined toform a 5 to 8-membered carbocyclic or heterocyclic ring; further whereinthe aliphatic or aromatic portions of R₁ and R₂ are optionallysubstituted with from 1 to 4 substituents selected from the groupconsisting of halogen, cyano, nitro, C₁₋₄alkyl, C₂₋₆alkenyl,C₂₋₆alkynyl, aryl, C₁₋₆alkoxy, C₂₋₆alkenyloxy, C₂₋₆alkynyloxy, aryloxy,C₂₋₆alkoxycarbonyl, C₁₋₆alkylthio, C₁₋₆alkylsulfonyl, C₁₋₆alkylsulfinyl,oxo, imino, thiono, primary amino, carboxyl, C₁₋₆alkylamino,C₁₋₆dialkylamino, amido, nitrogen heterocycles, hydroxy, thiol andphosphorous.
 2. A polymer that comprises a stable cyclopropenium cationthat remains positively charged at a high pH, the polymer having thestructure:

wherein X₁₋₂ are independently selected from the group consisting of Cl,N, F, Br, and I; R₁₋₂ are independently selected from the groupconsisting of no atom, amino, aryl, heteroaryl, C₁₋₁₀alkoxy,C₂₋₁₀alkenyloxy, C₂₋₁₀alkynyloxy, C₁₋₁₀alkyl, C₃₋₁₀cycloalkyl,C₂₋₁₀alkenyl, C₃₋₁₀cycloalkenyl, C₂₋₁₀alkynyl, halogen, aryloxy,heteroaryloxy, C₂₋₁₀alkoxycarbonyl, C₁₋₁₀alkylthio, C₂₋₁₀alkenylthio,C₂₋₁₀alkynylthio, C₁₋₁₀alkylsulfonyl, C₁₋₁₀alkylsulfinyl,aryl-C₁₋₁₀alkyl, heteroaryl-C₁₋₁₀alkyl, aryl-C₁₋₁₀heteroalkyl,heteroaryl-C₁₋₁₀heteroalkyl, a phosphorous group, a silicon group and aboron group, wherein R₁ and R₂ are optionally combined to form a 5 to8-membered carbocyclic or heterocyclic ring; further wherein thealiphatic or aromatic portions of R₁ and R₂ are optionally substitutedwith from 1 to 4 substituents selected from the group consisting ofhalogen, cyano, nitro, C₁₋₄alkyl, C₂₋₆alkenyl, C₂₋₆alkynyl, aryl,C₁₋₆alkoxy, C₂₋₆alkenyloxy, C₂₋₆alkynyloxy, aryloxy, C₂₋₆alkoxycarbonyl,C₁₋₆alkylthio, C₁₋₆alkylsulfonyl, C₁₋₆alkylsulfinyl, oxo, imino, thiono,primary amino, carboxyl, C₁₋₆alkylamino, C₁₋₆dialkylamino, amido,nitrogen heterocycles, hydroxy, thiol and phosphorous; wherein X₁R₁R₂and X₂R₁R₂ are, individually, Cl, F, Br, I, or N bonded to R₁ and R₂,

 represents a suitable linking group; and n is an integer.
 3. Thepolymer according to claim 2, wherein the polymer is selected from thegroup consisting of a linear polymer, a branched polymer, a cross-linkedpolymer, and a dendritic polymer.
 4. The polymer according to claim 2,wherein the polymer is a homopolymer or a heteropolymer.
 5. The polymeraccording to claim 4, wherein the heteropolymer is selected from thegroup consisting of a random copolymer, a block copolymer, and a graftcopolymer.
 6. The polymer according to claim 2, wherein the polymerbackbone is formed from a monomer comprising a group selected from thegroup consisting of ethylene, propylene, styrene, (meth)acrylate, vinylchloride, urethane, ethylene terephthalate, ester, amide, norbornene,silicon, ether, and combinations thereof.
 7. The polymer according toclaim 2, wherein the cyclopropenium cation remains positively charged ina pH range from 0 to greater than
 14. 8. The polymer according to claim2, wherein the cyclopropenium cation remains positively charged in a pHrange from 8 to
 13. 9. The A polymer that comprises a stablecyclopropenium cation that remains positively charged at a high pH, thepolymer having the structure:

wherein X₁₋₂ are independently selected from the group consisting of Cl,N, F, Br, and I; R₁₋₂ are independently selected from the groupconsisting of no atom, amino, aryl, heteroaryl, C₁₋₁₀alkoxy,C₂₋₁₀alkenyloxy, C₂₋₁₀alkynyloxy, C₁₋₁₀alkyl, C₃₋₁₀cycloalkyl,C₂₋₁₀alkenyl, C₃₋₁₀cycloalkenyl, C₂₋₁₀alkynyl, halogen, aryloxy,heteroaryloxy, C₂₋₁₀alkoxycarbonyl, C₁₋₁₀alkylthio, C₂₋₁₀alkenylthio,C₂₋₁₀alkynylthio, C₁₋₁₀alkylsulfonyl, C₁₋₁₀alkylsulfinyl,aryl-C₁₋₁₀alkyl, heteroaryl-C₁₋₁₀alkyl, aryl-C₁₋₁₀heteroalkyl,heteroaryl-C₁₋₁₀heteroalkyl, a phosphorous group, a silicon group and aboron group, wherein R₁ and R₂ are optionally combined to form a 5 to8-membered carbocyclic or heterocyclic ring; further wherein thealiphatic or aromatic portions of R₁ and R₂ are optionally substitutedwith from 1 to 4 substituents selected from the group consisting ofhalogen, cyano, nitro, C₁₋₄alkyl, C₂₋₆alkenyl, C₂₋₆alkynyl, aryl,C₁₋₆alkoxy, C₂₋₆alkenyloxy, C₂₋₆alkynyloxy, aryloxy, C₂₋₆alkoxycarbonyl,C₁₋₆alkylthio, C₁₋₆alkylsulfonyl, C₁₋₆alkylsulfinyl, oxo, imino, thiono,primary amino, carboxyl, C₁₋₆alkylamino, C₁₋₆dialkylamino, amido,nitrogen heterocycles, hydroxy, thiol and phosphorous; wherein X₁R₁R₂and X₂R₁R₂ are, individually, Cl, F, Br, I, or N bonded to R₁ and R₂,

 represents a suitable linking group; and n is an integer, wherein R₁₋₂are independently selected from the group consisting of

and combinations thereof.
 10. A polymer selected from the groupconsisting of:

wherein: R₁₋₂ are independently selected from the group consisting of noatom, amino, aryl, heteroaryl, C₁₋₁₀alkoxy, C₂₋₁₀alkenyloxy,C₂₋₁₀alkynyloxy, C₁₋₁₀alkyl, C₃₋₁₀cycloalkyl, C₂₋₁₀alkenyl,C₃₋₁₀cycloalkenyl, C₂₋₁₀alkynyl, halogen, aryloxy, heteroaryloxy,C₂₋₁₀alkoxycarbonyl, C₁₋₁₀alkylthio, C₂₋₁₀alkenylthio, C₂₋₁₀alkynylthio,C₁₋₁₀alkylsulfonyl, C₁₋₁₀alkylsulfinyl, aryl-C₁₋₁₀alkyl,heteroaryl-C₁₋₁₀alkyl, aryl-C₁₋₁₀heteroalkyl,heteroaryl-C₁₋₁₀heteroalkyl, a phosphorous group, a silicon group and aboron group, wherein R₁ and R₂ are optionally combined to form a 5 to8-membered carbocyclic or heterocyclic ring; further wherein thealiphatic or aromatic portions of R₁ and R₂ are optionally substitutedwith from 1 to 4 substituents selected from the group consisting ofhalogen, cyano, nitro, C₁₋₄alkyl, C₂₋₆alkenyl, C₂₋₆alkynyl, aryl,C₁₋₆alkoxy, C₂₋₆alkenyloxy, C₂₋₆alkynyloxy, aryloxy, C₂₋₆alkoxycarbonyl,C₁₋₆alkylthio, C₁₋₆alkylsulfonyl, C₁₋₆alkylsulfinyl, oxo, imino, thiono,primary amino, carboxyl, C₁₋₆alkylamino, C₁₋₆dialkylamino, amido,nitrogen heterocycles, hydroxy, thiol and phosphorous; and n is aninteger.
 11. A dendrimer having (1) a cationic core comprising atri-functional cyclopropenium monomer and (2) at least two ordereddendritic core branches which (a) are covalently bonded to the cationiccore, (b) extend through at least two generations, and (c) have at least3 terminal groups per core branch.
 12. The dendrimer according to claim11, wherein the cationic core is:


13. The dendrimer according to claim 11, wherein the dendritic corebranches are independently selected from the group consisting of:


14. A drug delivery vehicle comprising a stable cationic dendriticpolymer made by a process for making a dendritic polymer comprising thesteps of: a. providing a first functionalized compound comprising acyclopropenium ion, which has a reactive group at each position of thering; and b. grafting a second functionalized compound onto eachreactive group of the first functionalized compound such that chemicalbonds are formed between the first functionalized compound and thesecond functionalized compound at the reactive groups, the secondfunctionalized compound including reactive groups capable of formingbonds with the reactive groups on the cyclopropenium ion, and whereinthe bonds are formed through a click chemistry mechanism.
 15. Thecompound according to claim 1, wherein the compound is self-assemblingwhen contacted with a substrate, either as a consequence of interactionsbetween molecules of the compounds, or of interactions between thecompound and the surface of the substrate.
 16. A polymer that comprisesa stable cyclopropenium cation that remains positively charged at a highpH, the polymer having the structure:

wherein X₁₋₂ are independently selected from the group consisting of Cl,N, F, Br, and I; R₁₋₂ are independently selected from the groupconsisting of no atom, amino, aryl, heteroaryl, C₁₋₁₀alkoxy,C₂₋₁₀alkenyloxy, C₂₋₁₀alkynyloxy, C₁₋₁₀alkyl, C₃₋₁₀cycloalkyl,C₂₋₁₀alkenyl, C₃₋₁₀cycloalkenyl, C₂₋₁₀alkynyl, halogen, aryloxy,heteroaryloxy, C₂₋₁₀alkoxycarbonyl, C₁₋₁₀alkylthio, C₂₋₁₀alkenylthio,C₂₋₁₀alkynylthio, C₁₋₁₀alkylsulfonyl, C₁₋₁₀alkylsulfinyl,aryl-C₁₋₁₀alkyl, heteroaryl-C₁₋₁₀alkyl, aryl-C₁₋₁₀heteroalkyl,heteroaryl-C₁₋₁₀heteroalkyl, a phosphorous group, a silicon group and aboron group, wherein R₁ and R₂ are optionally combined to form a 5 to8-membered carbocyclic or heterocyclic ring; further wherein thealiphatic or aromatic portions of R₁ and R₂ are optionally substitutedwith from 1 to 4 substituents selected from the group consisting ofhalogen, cyano, nitro, C₁₋₄alkyl, C₂₋₆alkenyl, C₂₋₆alkynyl, aryl,C₁₋₆alkoxy, C₂₋₆alkenyloxy, C₂₋₆alkynyloxy, aryloxy, C₂₋₆alkoxycarbonyl,C₁₋₆alkylthio, C₁₋₆alkylsulfonyl, C₁₋₆alkylsulfinyl, oxo, imino, thiono,primary amino, carboxyl, C₁₋₆alkylamino, C₁₋₆dialkylamino, amido,nitrogen heterocycles, hydroxy, thiol and phosphorous; wherein X₁R₁R₂and X₂R₁R₂ are, individually, Cl, F, Br, I, or N bonded to R₁ and R₂,

 represents a suitable linking group; and n is an integer, wherein R₁₋₂are independently selected from the group consisting of

and combinations thereof.
 17. A polymer of the formula:

wherein: R₁₋₂ are independently selected from the group consisting of noatom, amino, aryl, heteroaryl, C₁₋₁₀alkoxy, C₂₋₁₀alkenyloxy,C₂₋₁₀alkynyloxy, C₁₋₁₀alkyl, C₃₋₁₀cycloalkyl, C₂₋₁₀alkenyl,C₃₋₁₀cycloalkenyl, C₂₋₁₀alkynyl, halogen, aryloxy, heteroaryloxy,C₂₋₁₀alkoxycarbonyl, C₁₋₁₀alkylthio, C₂₋₁₀alkenylthio, C₂₋₁₀alkynylthio,C₁₋₁₀alkylsulfonyl, C₁₋₁₀alkylsulfinyl, aryl-C₁₋₁₀alkyl,heteroaryl-C₁₋₁₀alkyl, aryl-C₁₋₁₀heteroalkyl,heteroaryl-C₁₋₁₀heteroalkyl, a phosphorous group, a silicon group and aboron group, wherein R₁ and R₂ are optionally combined to form a 5 to8-membered carbocyclic or heterocyclic ring; further wherein thealiphatic or aromatic portions of R₁ and R₂ are optionally substitutedwith from 1 to 4 substituents selected from the group consisting ofhalogen, cyano, nitro, C₁₋₄alkyl, C₂₋₆alkenyl, C₂₋₆alkynyl, aryl,C₁₋₆alkoxy, C₂₋₆alkenyloxy, C₂₋₆alkynyloxy, aryloxy, C₂₋₆alkoxycarbonyl,C₁₋₆alkylthio, C₁₋₆alkylsulfonyl, C₁₋₆alkylsulfinyl, oxo, imino, thiono,primary amino, carboxyl, C₁₋₆alkylamino, C₁₋₆dialkylamino, amido,nitrogen heterocycles, hydroxy, thiol and phosphorous; and n is aninteger.
 18. The stable, polycationic compound of claim 1, wherein theprocess comprises emulsion polymerization.